Hydrogenated norbornene-based ring-opening polymerization polymer, resin composition, and molded object

ABSTRACT

A hydrogenated norbornene ring-open polymer obtained by hydrogenating 80% or more of main-chain carbon-carbon double bonds of a ring-open polymer obtained by ring-opening polymerization of 2-norbornene. The hydrogenated norbornene ring-open polymer has a weight average molecular weight determined by gel permeation chromatography (GPC) of 50,000 to 200,000, a molecular weight distribution of 1.5 to 10.0, and a melting point of 110 to 145° C. A hydrogenated norbornene ring-open polymer obtained by hydrogenating 80% or more of carbon-carbon double bonds of a ring-open polymer obtained by ring-opening copolymerization of 2-norbornene and a substituent-containing norbornene monomer, wherein the proportion of a repeating unit (A) derived from the 2-norbornene with respect to all repeating units is 90 to 99 wt % and the proportion of a repeating unit (B) derived from the substituent-containing norbornene monomer with respect to all repeating units is 1 to 10 wt %. A resin composition and a molding material.

This application is a divisional of U.S. application Ser. No.12/439,360, filed on Feb. 27, 2009, which is a National Stage ofInternational Application No. PCT/JP2007/67043, filed on Aug. 31, 2007,which claims priority to Japanese priority application No. 2006-236627filed on Aug. 31, 2006, Japanese priority application No. 2006-237000filed on Aug. 31, 2006, Japanese priority application No. 2006-266680filed on Sep. 29, 2006 and Japanese priority application No. 2006-266683filed on Sep. 29, 2006, Japanese priority application No. 2006-266889filed Sep. 29, 2006, Japanese priority application No. 2006-269332 filedSep. 29, 2006, Japanese priority application No. 2006-342808 filed Dec.20, 2006, Japanese priority application No. 2006-342872 filed Dec. 20,2006, Japanese priority application No. 2006-355191 filed Dec. 28, 2006,which are hereby incorporated by reference.

TECHNICAL FIELD

The present invention relates to a hydrogenated norbornene ring-openpolymer exhibiting excellent steam barrier properties, heat resistance,oil resistance, mechanical properties, processability, and the likewhich are properties demanded in recent years in the fields ofinformation processing, food industries, medical supplies, engineeringworks, and the like, a resin composition comprising the hydrogenatednorbornene ring-open polymer and an antioxidant, and a molded articleobtained by molding the hydrogenated norbornene ring-open polymer or theresin composition.

BACKGROUND ART

Since a hydrogenated norbornene ring-open polymer has excellenttransparency and a low birefringence, application of the polymer as aresin material for optical lenses or optical sheets has been proposed(Patent Documents 1 and 2). In addition, since the polymer exhibitsexcellent fluidity in a molten state and also has excellent elusionproperties and chemical resistance, application of the polymer as aresin material for other than optical application such as a packingfilm, a medical container, and the like has been proposed (PatentDocuments 3 and 4). However, since many hydrogenated norbornenering-open polymers are amorphous, their moisture proofing properties,anti-sebum properties, solvent resistance, and the like areinsufficient. Improvement of these properties has been desired.

As a hydrogenated norbornene ring-open polymer having crystallinity(i.e. having a melting point), crystalline hydrogenated products of anorbornene ring-open polymer containing a repeating unit of norbornenemonomers having 3 or more rings are known (Patent Documents 5 to 7).Resin films or sheets obtained from the hydrogenated norbornenering-open polymers described in these documents are excellent intransparency, heat resistance, and chemical resistance, as well asmechanical strength. However, these crystalline hydrogenated norbornenering-open polymers have poor solubility in solvents and deposit from thesolvent after hydrogenating the ring-open polymer, sometime making itdifficult to sufficiently purify the polymer by removing residualcatalysts and the like. In addition, the film molded from thehydrogenated norbornene ring-open polymer did not fully satisfy therequirement for moisture permeability.

Non-patent Documents 1 and 2 propose hydrogenated norbornene ring-openpolymers possessing a certain degree of crystallinity. However, thesedocuments do not specifically describe the properties of the polymers.Among the specifically disclosed polymers, those having a high molecularweight and a narrow molecular weight distribution exhibited difficultyin controlling the film thickness when the film is produced. Films madefrom the polymer having a small molecular weight had a small tensilebreaking elongation, indicating that the polymer has a problem ofmechanical properties when made into a film. Furthermore, since thehydrogenation degree is not necessarily enough, molded products madefrom the polymer are easily burned.

Along with high integration of semiconductor chips and liquid crystaldisplay devices in the electronic fields, quality degradation due tomixing of contaminants such as fine particles, moisture, and organicsubstances during the manufacturing process poses a serious problem.Therefore, it is necessary to store and transport precision substratessuch as a silicon wafer substrate, a liquid crystal display substrate,and the like used for production of these parts under an environmentwhere the above-mentioned contaminants are reduced to an amount as smallas possible. For this reason, a method of storing and transporting theseprecision substrates in a state isolated from the outside environment byutilizing an airtight container of which the inside is highly purified(a wafer carrier for semiconductor production) is used.

A method of filling the container with clean air or an inert gas inorder to prevent contaminants such as fine particles from adhering tothe precision substrate stored in the container has also been employed.In order to respond to the recent demand for further low contamination,a method of evacuating the internal atmosphere of the container toprovide vacuum or reduced pressure conditions has been proposed. Thecontainer of which the internal atmosphere is evacuated not only must beairtight and pressure resistant, but also the container material itselfmust not discharge contaminants such as moisture and organic substances.

As a container satisfying these requirements, a metal container and acontainer made from a thermoplastic resin having excellent chemicalresistance and low water absorptivity such as polypropylene (PP),polytetrafluoroethylene (PTFE), perfluoroalkoxy fluororesin (PFA), orthe like are known.

However, a metal container is heavy, cannot allow observation of theprecision substrates stored therein, and has a high manufacturing cost.PP is opaque and has poor dimensional accuracy and heat resistance. PTFEis not only opaque and has poor dimensional accuracy, but also does notallow injection molding, making mass production difficult. The PTFEproduct is therefore expensive. PFA has insufficient transparency andpoor dimensional accuracy, and it is difficult to synthesize PFA and tomanufacture the product in a large scale. The PFA product is thus alsoexpensive.

As a molding material which solves these problems, a thermoplasticnorbornene resin which can be molded by injection molding and hasexcellent heat resistance, moisture resistance, chemical resistance,transparency, and the like is attracting attention in recent years.

For example, a thermoplastic resin container formed from a cycloolefinresin is proposed in Patent Document 8. The Patent Document 8 describesthat a hydrogenated norbornene ring-open polymer is preferable as acycloolefin resin due to the small content of impurities such as lowmolecular weight components, catalyst residues, metals, and the like inthe resin and also due to high transparency.

Patent Document 9 proposes a material for producing semiconductorsformed from a thermoplastic saturated norbornene resin having a contactsurface of 18.6 kgf/cm² at a load deflecting temperature of 70° C.Patent Document 10 proposes a container for precision substrates madefrom a thermoplastic resin and having one or more components which havespecific properties. A hydrogenated norbornene ring-open polymer and thelike are given as a preferable thermoplastic resin.

However, when a wafer carrier for semiconductor production is fabricatedusing the thermoplastic resin molding material described in these PatentDocuments, there is a problem that the surface of the semiconductors inthe carrier is contaminated with an organic substance discharged fromthe molded article. In addition, when the wafer is inserted into orremoved from the carrier, the carrier may be caused to come into contactwith the wafer and produce a resin powder (foreign matter) whichcontaminates the wafer.

In the field of medical supplies and food packing, packing materials formedical supplies such as an infusion solution bag, a blood bag, a bottlefor medicine, a cell used for analysis, and a medical test tube, as wellas packing materials for food such as bean paste, soy sauce, andmayonnaise are widely used. These packing materials are required topossess transparency, chemical resistance, impact resistance, capabilityof being repeatedly sterilized, steam barrier properties, and the like.In order to satisfy these requirements, a number of packing materialsfor medical supplies and foods using a synthetic resin such as athermoplastic norbornene resin having excellent transparency or chemicalresistance have been proposed.

For example, Patent Document 11 proposes a packing container for medicalsupplies and foods of which the wall is made of a multilayer laminate,at least one layer being made of a thermoplastic norbornene polymer.

Patent Document 12 discloses a molded article prepared by laminating agas barrier resin layer of a partially saponified polyvinyl acetate onthe surface of a thermoplastic norbornene resin molded article.

However, all the thermoplastic norbornene resins described in theseDocuments are amorphous materials which have insufficient impactresistance and oil resistance when used as a packing material formedical supplies. Moreover, the packing container for medical suppliesand foods described in Patent Document 11 has poor steam barrierproperties. The molded article described in Patent Document 12, in whichthermoplastic norbornene resin has poor steam barrier properties, has aproblem of degradation of oxygen barrier properties due to denaturing ofthe gas barrier resin layer by water in a high temperature and highhumidity environment.

On the other hand, Patent Document 13 proposes a film or a sheetobtained by molding a norbornene ring-open polymer having a meltingpoint or a hydrogenated norbornene ring-open polymer having a meltingpoint obtained by hydrogenating the carbon-carbon double bonds in thering-open polymer.

However, the hydrogenated dicyclopentadiene ring-open polymer having amelting point which is specifically disclosed in this Patent Documentcan be molded only with difficulty due to unduly high melting point of270° C. or more. In addition, the resulting molded product has poorsteam barrier properties and mechanical properties such as impactresistance.

Blister molded articles such as a press-through package (PTP) have beenmanufactured by producing a resin sheet (sheet for blister mold) andmolding the sheet by a heat molding method such as vacuum molding orpressure molding.

Outstanding moldability, damp proofing (steam barrier) properties,impact resistance, oil resistance, and the like are required for suchblister molded articles. In order to satisfy these requirements, anumber of blister molded articles made of a synthetic resin such as athermoplastic norbornene resin have been proposed.

For example, Patent Document 14 discloses a press through package (PTP)with a packed material contained therein. The package is prepared byenclosing the material to be packed in a pocket provided on a sheet of athermoplastic norbornene resin and blocking the pocket opening of thesheet with another sheet.

Patent Document 15 discloses a multilayer sheet for packing drugsrequiring high moisture proofing properties. The sheet is made from (A)an amorphous polyolefin having a heat distortion temperature of 100° C.or less, which is a copolymer of a product of the Diels-Alder additionreaction of cyclopentadiene (or a derivative thereof) and norbornadiene(or a derivative thereof) and an unsaturated monomer and (B)polypropylene, wherein a layer of the polypropylene (B) is laminated onat least one side of the amorphous polyolefin resin layer (A).

However, all thermoplastic norbornene resins described in theseDocuments are amorphous resins, which may sometimes have insufficientmechanical strength, heat resistance, and oil resistance when used as ablister molded article. The PTP described in Patent Document 14 maybecome whitened by adhesion of sebum during use, and the high moistureproofing multilayer sheet for packing drugs described in Patent Document15 has a problem of poor steam barrier properties.

In order to obviate these problems, Patent Document 16 proposes a filmor a sheet formed from a norbornene ring-open polymer having a meltingpoint or a hydrogenated norbornene ring-open polymer having a meltingpoint obtained by hydrogenating the carbon-carbon double bonds in thering-open polymer.

However, the hydrogenated dicyclopentadiene ring-open polymer having amelting point which is specifically disclosed in this Patent Documentcan be molded only with difficulty due to unduly high melting point of270° C. or more. In addition, the resulting molded product may have poorsteam barrier properties and mechanical properties.

On the other hand, Patent Document 17 discloses a blow-molded articleprepared by blow molding of a norbornene polymer having a melting point.The norbornene polymer having a melting point described in PatentDocument 17 is a crystalline polymer. Various hydrogenated ring-openpolymers of norbornene monomers are mentioned as the norbornene polymerhaving a melting point in Patent Document 17. However, the Documentspecifically describes only a hydrogenated ring-open polymer ofdicyclopentadiene. The hydrogenated dicyclopentadiene ring-open polymeris a polymer having a high melting point of 200 to 400° C.

Therefore, in the blow molding process shown in examples of PatentDocument 17, the hydrogenated dicyclopentadiene ring-open polymer isextruded from a biaxial extruder at a barrel temperature of 290 to 300°C. and a die temperature of about 320° C. to produce a molten parison.Molding at such a high temperature not only subjects the molding machineto a significant load, but also tends to produce resin burning(discoloration). Although the resulting blow-molded container isexcellent in heat resistance, oil resistance, chemical resistance, andthe like, the steam barrier properties are not necessarily sufficient.In addition, since the hydrogenated dicyclopentadiene ring-open polymercan be dissolved in an organic solvent only with difficulty,purification of the product is difficult and the product has a problemof elution of metals derived from the catalyst.

The above-mentioned Non-patent Document 1 reports that a crystallinethermoplastic polymer with a melting point of 141° C. was obtained byhydrogenating an amorphous polynorbornene having a trans content of 80%and a weight average molecular weight (Mw) of 2,000,000.

Non-patent Document 2 reports the crystal structure and melting point ofa block copolymer of hydrogenated polynorbornene and hydrogenatedpolyethylidene norbornene (hPN/hPEN).

However, since the hydrogenated norbornene ring-open polymers disclosedby Non-patent Documents 1 and 2 have a large number average molecularweight (Mn) and a narrow molecular weight distribution (Mw/Mn), it isdifficult to precisely control the thickness of the container formed ifthe polymers are molded by blow molding. In fact, neither Non-patentDocument 1 nor Non-patent Document 2 describes production of a moldedarticle by blow molding of the hydrogenated polymers.

-   [Patent Document 1] JP-A-60-26024-   [Patent Document 2] JP-A-9-263627-   [Patent Document 3] JP-A-2000-313090-   [Patent Document 4] JP-A-2003-183361-   [Patent Document 5] JP-A-2000-201826-   [Patent Document 6] JP-A-2000-393316-   [Patent Document 7] JP-A-2006-52333-   [Patent Document 8] JP-A-11-74337-   [Patent Document 9] JP-A-2002-217279-   [Patent Document 10] WO 2003/021665-   [Patent Document 11] JP-A-4-276253-   [Patent Document 12] JP-A-2002-127315-   [Patent Document 13] JP-A-2002-194067-   [Patent Document 14] JP-A-6-278706-   [Patent Document 15] JP-A-7-178884-   [Patent Document 16] JP-A-2002-194067-   [Patent Document 17] JP-A-2002-249554-   [Non-patent Document 1] Polymer International, Vol. 34, pp. 49-57    (1994)-   [Non-patent Document 2] Macromolecules, Vol. 37, pp. 7278-7284    (2004)

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention

The present invention has been achieved in view of this situation ingeneral technology and has an object of providing the following (a) to(g):

(a) a hydrogenated norbornene ring-open polymer which can be used as aresin material exhibiting excellent steam barrier properties, heatresistance, oil resistance, mechanical properties, processability, andthe like which are properties demanded in recent years in the fields ofinformation processing, food industries, medical supplies, engineeringworks, and the like in recent years, and a resin composition comprisingthe hydrogenated norbornene ring-open polymer,(b) a resin film or sheet obtainable by molding the above hydrogenatednorbornene ring-open polymer or resin composition,(c) a molded article useful as a material for processing electronicparts obtainable by molding the above hydrogenated norbornene ring-openpolymer or resin composition,(d) a multilayer laminate having excellent damp proofing (steam barrier)properties, mechanical properties such as impact resistance, and oilresistance, as well as excellent gas barrier properties in a hightemperature and high humidity environment (when the multilayer laminateincludes at least one layer containing a gas barrier resin), and apacking material obtained by fabricating the multilayer laminate,(e) a medical supply packing material having steam barrier properties,mechanical properties, oil resistance, pliability, and moldability, andparticularly excellent steam barrier properties at a high temperature,(f) a blister molding sheet having excellent steam barrier properties,oil resistance, and processability, particularly having excellent steambarrier properties at a high temperature, and a blister-molded articleobtained by molding the blister molding sheet, and(g) a monolayer or multilayer blow-molded container, each layercontaining a hydrogenated norbornene ring-open polymer, having excellentsteam barrier properties, heat resistance, oil resistance, mechanicalproperties, processability, and the like, and having a small haze.

In order to achieve the above object, a first aspect of the presentinvention provides a hydrogenated norbornene ring-open polymer, a resincomposition, a resin sheet, a resin film, and a sheet described in (1)to (7) below.

(1) A hydrogenated norbornene ring-open polymer obtained byhydrogenating 80% or more of main-chain carbon-carbon double bonds of aring-open polymer which is obtained by ring-opening polymerization of2-norbornene, the hydrogenated norbornene ring-open polymer having aweight average molecular weight (Mw) determined by gel permeationchromatography (GPC) of 50,000 to 200,000, a molecular weightdistribution (Mw/Mn) of 1.5 to 10.0, and a melting point of 110 to 145°C.(2) A hydrogenated norbornene ring-open polymer obtained byhydrogenating 80% or more of carbon-carbon double bonds of a ring-openpolymer which is obtained by ring-opening copolymerization of2-norbornene and a substituent-containing norbornene monomer, theproportion of a repeating unit (A) derived from the 2-norbornene withrespect to all repeating units being 90 to 99 wt % and the proportion ofa repeating unit (B) derived from the substituent-containing norbornenemonomer with respect to all repeating units being 1 to 10 wt %, and thehydrogenated norbornene ring-open polymer having a melting point of 110to 145° C.(3) The hydrogenated norbornene ring-open polymer according to (2),having a weight average molecular weight (Mw) determined by gelpermeation chromatography (GPC) of 50,000 to 200,000.(4) The hydrogenated norbornene ring-open polymer according to (2),having a ratio (Mw/Mn) of the weight average molecular weight (Mw) tothe number average molecular weight (Mn) of 1.5 to 10.0.(5) A resin composition comprising the hydrogenated norbornene ring-openpolymer of (1) or (2).(6) The resin composition according to (5), further comprising 0.01 to 1part by weight of an antioxidant per 100 parts by weight of thehydrogenated norbornene ring-open polymer.(7) A resin film or sheet obtained by molding the hydrogenatednorbornene ring-open polymer described in (1) or (2) or the resincomposition described in (5).

According to a second aspect of the present invention, molding materialsand molded articles described in (8) to (12) below are provided.

(8) A molding material comprising a hydrogenated norbornene ring-openpolymer obtained by hydrogenating 80% or more of carbon-carbon doublebonds of a ring-open polymer which is obtained by ring-openingpolymerization of 2-norbornene or a substituent-containing norbornenemonomer, the proportion of a repeating unit (A) derived from the2-norbornene with respect to all repeating units being 90 to 100 wt %and the proportion of a repeating unit (B) derived from thesubstituent-containing norbornene monomer with respect to all repeatingunits being 0 to 10 wt %, and the hydrogenated norbornene ring-openpolymer having a melting point of 110 to 145° C., and the amount oforganic substances discharged from the molding material when heated at80° C. for 60 minutes being not more than 1 ppm.(9) The molding material according to (8), wherein the content oftransition metals is not more than 1 ppm.(10) A molded article obtained by molding the molding material accordingto (8).(11) The molded article according to (10), which is a material forprocessing electronic parts.(12) The molded article according to (11), which is a wafer carrier forsemiconductor production.

According to a third aspect of the present invention, multilayerlaminates and packing materials described in (13) to (17) below areprovided.

(13) A multilayer laminate having two or more resin layers of which atleast one layer is a layer of a hydrogenated norbornene ring-openpolymer obtained by hydrogenating 80% or more of carbon-carbon doublebonds of a ring-open polymer which is obtained by ring-openingpolymerization of 2-norbornene or a monomer mixture of 2-norbornene anda substituent-containing norbornene monomer, the proportion of arepeating unit (A) derived from the 2-norbornene with respect to allrepeating units being 90 to 100 wt % and the proportion of a repeatingunit (B) derived from the substituent-containing norbornene monomer withrespect to all repeating units being 0 to 10 wt %, and the hydrogenatednorbornene ring-open polymer having a melting point of 110 to 145° C.(14) The multilayer laminate according to (13), wherein at least onelayer is a layer containing a gas barrier resin.(15) The multi layer laminate according to (13), wherein the gas barrierresin is an ethylene-vinyl alcohol copolymer.(16) The multi layer laminate according to (13), wherein at least onelayer is a layer containing at least one resin selected from the groupconsisting of a polyolefin resin, a polyamide resin, and a polyesterresin.(17) A packing material obtained by fabricating the multilayer laminateaccording to (13).

According to a fourth aspect of the present invention, a medical supplypacking material described in (18) to (21) below is provided.

(18) A medical supply packing material having at least one resin layerwhich is a layer of a hydrogenated norbornene ring-open polymer obtainedby hydrogenating 80% or more of carbon-carbon double bonds of aring-open polymer which is obtained by ring-opening polymerization of2-norbornene or a monomer mixture of 2-norbornene and asubstituent-containing norbornene monomer, the proportion of a repeatingunit (A) derived from the 2-norbornene with respect to all repeatingunits being 90 to 100 wt % and the proportion of a repeating unit (B)derived from the substituent-containing norbornene monomer with respectto all repeating units being 0 to 10 wt %, and the hydrogenatednorbornene ring-open polymer having a melting point of 110 to 145° C.(19) The medical supply packing material according to (18), furthercomprising at least one polyolefin resin layer.(20) The medical supply packing material according to (19), wherein thepolyolefin resin layer is a polyethylene resin layer.(21) The medical supply packing material according to (18), which is aninfusion solution bag.

According to a fifth aspect of the present invention, a blister moldingsheet and a blister molded article described in (22) to (25) below areprovided.

(22) A blister molding sheet having at least one resin layer of ahydrogenated norbornene ring-open polymer obtained by hydrogenating 80%or more of carbon-carbon double bonds of a ring-open polymer which isobtained by ring-opening polymerization of 2-norbornene or a monomermixture of 2-norbornene and a substituent-containing norbornene monomer,the proportion of a repeating unit (A) derived from the 2-norbornenewith respect to all repeating units being 90 to 100 wt % and theproportion of a repeating unit (B) derived from thesubstituent-containing norbornene monomer with respect to all repeatingunits being 0 to 10 wt %, and the hydrogenated norbornene ring-openpolymer having a melting point of 110 to 145° C.(23) The blister molding sheet according to (22), which is a multilayerlaminate comprising at least one polyolefin resin layer.(24) The blister molding sheet according to (23), wherein the polyolefinresin is a polypropylene resin.(25) A blister molded article obtained by molding the blister moldingsheet according to (22).

According to a sixth aspect of the present invention, a blow-moldedcontainer described in (26) below is provided.

(26) A blow-molded container having at least one resin layer of ahydrogenated norbornene ring-open polymer obtained by hydrogenating 80%or more of carbon-carbon double bonds of a ring-open polymer which isobtained by ring-opening polymerization of 2-norbornene or a monomermixture of 2-norbornene and a substituent-containing norbornene monomer,the proportion of a repeating unit (A) derived from the 2-norbornenewith respect to all repeating units being 90 to 100 wt % and theproportion of a repeating unit (B) derived from thesubstituent-containing norbornene monomer with respect to all repeatingunits being 0 to 10 wt %, and the hydrogenated norbornene ring-openpolymer having a melting point of 110 to 145° C.

Effect of the Invention

According to the present invention, a hydrogenated norbornene ring-openpolymer which can be used as a resin material exhibiting excellent steambarrier properties, heat resistance, oil resistance; mechanicalproperties, processability, and the like which are properties demandedin recent years in the fields of information, food industries, medicalsupplies, engineering works, and the like, a resin compositioncomprising the hydrogenated norbornene ring-open polymer, and a resinfilm or resin sheet obtained by molding the resin composition can beobtained.

According to the present invention, a molding material having excellentheat resistance, discharging only a minimal amount of organic compounds,and generating only a very slight amount of foreign matters by frictionfrom a molded article, as well as a molded article obtained by moldingthe molding material can be provided.

The multilayer laminate and the packing material of the presentinvention have excellent steam barrier properties, mechanical propertiessuch as impact resistance, and oil resistance, and when possessing atleast one layer containing a gas barrier resin, have excellent gasbarrier properties in a high temperature and high humidity environment.

The medical supply packing material of the present invention hasexcellent steam barrier properties, mechanical properties, oilresistance, pliability, and moldability. The medical supply packingmaterial particularly exhibits superior steam barrier properties at ahigh temperature.

The blister molding sheet and the blister-molded article of the presentinvention have excellent steam barrier properties, oil resistance, andprocessability. The steam barrier properties of the blister moldingsheet and the blister-molded article at a high temperature isparticularly excellent.

According to the present invention, a monolayer or multilayerblow-molded container, each layer containing a hydrogenated norbornenering-open polymer, having excellent steam barrier properties, heatresistance, oil resistance, mechanical properties, processability, andthe like, and having a small haze can be provided.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a perspective diagram of a wafer carrier for producing asemiconductor according to the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will be described in detail below.

1) Hydrogenated Norbornene Ring-Open Polymer

The hydrogenated norbornene ring-open polymer of the present inventionis a polymer described in either (I) or (II) below.

(I) A hydrogenated norbornene ring-open polymer obtained byhydrogenating 80% or more of main-chain carbon-carbon double bonds of aring-open polymer which is obtained by ring-opening polymerization of2-norbornene (hydrogenated 2-norbornene ring-open polymer), thehydrogenated 2-norbornene ring-open polymer having a weight averagemolecular weight (Mw) determined by gel permeation chromatography (GPC)of 50,000 to 200,000, a molecular weight distribution (Mw/Mn) of 1.5 to10, and a melting point of 110 to 145° C. (hereinafter may be referredto from time to time as “hydrogenated norbornene ring-open polymer(I)”).(II) A hydrogenated norbornene ring-open polymer obtained byhydrogenating 80% or more of carbon-carbon double bonds of a ring-openpolymer which is obtained by ring-opening polymerization of 2-norborneneand a substituent-containing norbornene monomer, the proportion of arepeating unit (A) derived from the 2-norbornene with respect to allrepeating units being 90 to 99 wt % and the proportion of a repeatingunit (B) derived from the substituent-containing norbornene monomer withrespect to all repeating units being 1 to 10 wt %, and the hydrogenatednorbornene ring-open polymer having a melting point of 110 to 145° C.(hereinafter may be referred to from time to time as “hydrogenatednorbornene ring-open polymer (II)”).

The proportion of the repeating unit (A) derived from 2-norbornene withrespect to all repeating units in the hydrogenated norbornene ring-openpolymer (II) of the present invention is 90 to 99 wt %, preferably 95 to99 wt %, and more preferably 97 to 99 wt %. The proportion of therepeating unit (B) derived from substituent-containing norbornenemonomer with respect to all repeating units is 1 to 10 wt %, preferably1 to 5 wt %, and more preferably 1 to 3 wt %.

If the proportion of the repeating unit (A) and the repeating unit (B)is in this range, the hydrogenated norbornene ring-open polymer has goodsolubility in solvents. Therefore, the polymer can be obtained withexcellent productivity and can be purified with ease. In addition, theresulting molded article may have good mechanical properties,transparency, heat resistance, and steam barrier properties.Furthermore, the resin discharges only a very small amount of organicsubstances and generates resin powder (foreign matter) by friction andthe like only with difficulty.

If the amount of the repeating unit (B) is too large, the heatresistance and steam barrier properties of the molded article may beimpaired. In addition, the amount of organic substances discharged fromthe resin may increase and the molded article tends to easily generateresin powder (foreign matter) by friction.

If the amount of the repeating unit (B) is too small, the solubility ofthe hydrogenated polymer in solvents decreases, resulting in poorproductivity of the polymer and difficulty in polymer purification. Inaddition, the mechanical properties of the molded article may beimpaired. Moreover, the resulting molded article may more easilygenerate resin powder (foreign matter) by friction.

2-Norbornene used in the present invention is a known compound. Thiscompound may be obtained by reacting cyclopentadiene and ethylene, forexample. Industrially available 2-norbornene usually containsimpurities.

As examples of the impurities, cyclopentadiene, norbornane,methylnorbornene, dimethyldicyclopentadiene, and the like can be given.Of these, methylnorbornene, dimethylcyclopentadiene, and the like aremonomers copolymerizable with 2-norbornene by ring-openingcopolymerization.

The impurities in 2-norbornene is usually less than 1 wt %, preferablyless than 0.8 wt %, and more preferably less than 0.5 wt %. The heatresistance of the hydrogenated norbornene ring-open polymer ismaintained at a high level when the content of impurities is within thisrange.

Since the 2-norbornene used may contain other monomers copolymerizablewith 2-norbornene by ring-opening copolymerization as mentioned above,the hydrogenated norbornene ring-open polymer (I) also contains aring-open copolymer which contains a small amount of other monomerscopolymerizable with 2-norbornene by ring-opening copolymerization. Theamount of the monomers copolymerizable with 2-norbornene in the polymeris usually not more than 1 wt %, preferably not more than 0.8 wt %, andmore preferably not more than 0.5 wt %.

The substituent-containing norbornene monomer used in the presentinvention is a compound which has a norbornene skeleton in the molecule(excluding 2-norbornene). The term “substituent-containing norbornenemonomer” used in the present invention includes norbornene compoundspossessing a condensed ring, in addition to 2-norbornene derivativeshaving a substituent.

As the substituent-containing norbornene monomer, a norbornene monomernot containing a ring condensable with a norbornene ring in themolecule, a polycyclic norbornene monomer having three or more rings,and the like can be given.

As examples of the norbornene monomer not containing a ring condensablewith a norbornene ring in the molecule, norbornenes having an alkylgroup such as 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene,5-hexylnorbornene, 5-decylnorbornene, 5-cyclohexylnorbornene, and5-cyclopentylnorbornene; norbornenes having an alkenyl group such as5-ethylidenenorbornene, 5-vinylnorbornene, 5-propenylnorbornene,5-cyclohexenylnorbornene, and 5-cyclopentenylnorbornene; norborneneshaving an aromatic ring such as 5-phenylnorbornene; norbornenes having apolar group containing an oxygen atom such as5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene,5-methyl-5-methoxycarbonylnorbornene,5-methyl-5-ethoxycarbonylnorbornene, norbornenyl-2-methylpropionate,norbornenyl-2-methyloctanate, 5-hydroxymethylnorbornene,5,6-di(hydroxymethyl)norbornene, 5,5-di(hydroxymethyl)norbornene,5-hydroxy-1-propylnorbornene, 5,6-dicarboxynorbornene, and5-methoxycarbonyl-6-carboxynorbornene; norbornenes having a polar groupcontaining a nitrogen atom such as 5-cyanonorbornene; and the like canbe given.

The polycyclic norbornene monomer having three or more rings is to anorbornene monomer having a norbornene ring and one or more ringscondensed with the norbornene ring in the molecule. As specificexamples, monomers shown by the following formulas (2) and (3) can begiven.

wherein R¹ and R² individually represent a hydrogen atom, a halogenatom, a substituted or unsubstituted hydrocarbon group having 1 to 20carbon atoms, or a substituent containing a silicon atom, an oxygenatom, or a nitrogen atom, R¹ and R² may bond together to form a ring,and R³ represents a substituted or unsubstituted divalent hydrocarbongroup having 1 to 20 carbon atoms.

wherein R⁴ to R⁷ individually represent a hydrogen atom, a halogen atom,a substituted or unsubstituted hydrocarbon group having 1 to 20 carbonatoms, or a substituent containing a silicon atom, an oxygen atom or anitrogen atom, wherein R⁴ and R⁶ may bond together to form a ring, and mis an integer of 1 or 2.

As specific examples of the monomer shown by the above formula (2),dicyclopentadiene, methyldicyclopentadiene, dimethyldicyclopentadiene,and tricyclo[5.2.1.0^(2,6)]dec-8-ene can be given. Norbornenederivatives having an aromatic ring such astetracyclo[9.2.1.0^(2,10).0^(3,8)]tetradeca-3,5,7,12-tetraene (alsocalled 1,4-methano-1,4,4a,9a-tetrahydro-9H-fluorene) andtetracyclo[10.2.1.0^(2,11).0^(4,9)]pentadeca-4,6,8,13-tetraene (alsocalled 1,4-methano-1,4,4a,9,9a,10-hexahydroanthracene) can also begiven.

As examples of the monomer shown by the above formula (3),tetracyclododecenes which are the compounds of the formula (3) in whichm=1 and hexacycloheptadecenes which are compounds of the formula (3) inwhich m=2 can be given.

As specific examples of tetracyclododecenes, tetracyclododecenesunsubstituted or substituted with an alkyl group such astetracyclododecene, 8-methyltetracyclododecene,8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, and8-cyclopentyltetracyclododecene; tetracyclododecenes having a doublebond outside of the ring such as 8-methylidenetetracyclododecene,8-ethylidenetetracyclododecene, 8-vinyltetracyclododecene,8-propenyltetracyclododecene, 8-cyclohexenyltetracyclododecene, and8-cyclopentenyltetracyclododecene; tetracyclododecenes having anaromatic ring such as 8-phenyltetracyclododecene; tetracyclododeceneshaving an oxygen-containing substituent such as8-methoxycarbonyltetracyclododecene,8-methyl-8-methoxycarbonyltetracyclododecene,8-hydroxymethyltetracyclododecene, 8-carboxytetracyclododecene,tetracyclododecene-8,9-dicarboxylic acid, andtetracyclododecene-8,9-dicarboxylic anhydride; tetracyclododeceneshaving a nitrogen-containing substituent such as8-cyanotetracyclododecene and tetracyclododecene-8,9-dicarboxylic acidimide; tetracyclododecenes having a halogen-containing substituent suchas 8-chlorotetracyclododecene; and tetracyclododecenes having asilicon-containing substituent such as8-trimethoxysilyltetracyclododecene can be given.

As specific examples of hexacycloheptadecenes, hexacycloheptadecenesunsubstituted or substituted with an alkyl group such ashexacycloheptadecene, 12-methylhexacycloheptadecene,12-ethylhexacycloheptadecene, 12-cyclohexylhexacycloheptadecene, and12-cyclopentylhexacycloheptadecene; hexacycloheptadecenes having adouble bond outside of the ring such as12-methylidenehexacycloheptadecene, 12-ethylidenehexacycloheptadecene,12-vinylhexacycloheptadecene, 12-propenylhexacycloheptadecene,12-cyclohexenylhexacycloheptadecene, and12-cyclopentenylhexacycloheptadecene; hexacycloheptadecenes having anaromatic ring such as 12-phenylhexacycloheptadecene;hexacycloheptadecenes having an oxygen-containing substituent such as12-methoxycarbonylhexacycloheptadecene,12-methyl-12-methoxycarbonylhexacycloheptadecene,12-hydroxymethylhexacycloheptadecene, 12-carboxyhexacycloheptadecene,hexacycloheptadecene-12,13-dicarboxylic acid, andhexacycloheptadecene-12,13-dicarboxylic anhydride; hexacycloheptadeceneshaving a nitrogen-containing substituent such as12-cyanohexacycloheptadecene and hexacycloheptadecene-12,13-dicarboxylicacid imide; hexacycloheptadecenes having a halogen-containingsubstituent such as 12-chlorohexacycloheptadecene; andhexacycloheptadecenes having a silicon-containing substituent such as12-trimethoxysilylhexacycloheptadecene can be given. These norbornenemonomers may be used either individually or in combination of two ormore.

In the case of providing the hydrogenated norbornene ring-open polymer(II), other monomers copolymerizable with the 2-norbornene andsubstituent-containing norbornene monomers may be used in combination.

As examples of the other monomer copolymerizable with 2-norbornenemonomer and substituent-containing norbornene monomers, monocyclicolefins such as cyclohexene, cycloheptene, and cyclooctene, andderivatives thereof; cyclic diener such as cyclohexadiene andcycloheptadiene, and derivatives thereof; and the like can be given.

(Ring-Opening Polymerization)

The ring-opening polymerization of 2-norbornene or the ring-openingcopolymerization of 2-norbornene and a substituent-containing norbornenemonomer may be carried out in the presence of a metathesispolymerization catalyst in a solvent or without using a solvent.

As the metathesis polymerization catalyst, a general metathesispolymerization catalyst which essentially consists of (a) a transitionmetal compound catalyst component and (b) a metallic compoundco-catalyst component described in JP-B-41-20111, JP-A-46-14910,JP-B-57-17883, JP-B-57-61044, JP-A-54-86600, JP-A-58-127728, andJP-A-1-240517; a living ring-opening metathesis catalyst such asSchrock-type polymerization catalyst (JP-A-7-179575, Schrock et al., J.Am. Chem. Soc., 1990, vol. 112, from page 3875), Grubbs polymerizationcatalyst (Fu et al., J. Am. Chem. Soc., 1993, Vol. 115, from page 9856),Nguyen et al., J. Am. Chem. Soc., 1992, vol 114, from page 3974; Grubbset al. WO 98/21214, etc.); and the like can be given.

Taking the molecular weight distribution of the polymer intoconsideration, a metathesis polymerization catalyst comprising (α) atransition metal compound catalyst component and (β) a metallic compoundco-catalyst component is preferable among these catalysts.

The transition metal compound catalyst components (α) are transitionmetal compounds of the groups 3 to 11 of the Periodic Table. As examplesof the specific transition metal compound, a halide, an oxyhalide, analkoxyhalide, an alkoxide, a carbonate, an (oxy)acetylacetonate, acarbonyl complex, an acetonitrile complex, and an hydride complex ofthese transition metals, derivatives of these compounds, and complexcompounds of these, which are obtained by a complexing agent such asP(C₆H₅)₅ and the like can be given.

As specific examples, TiCl₄, TiBr₄, VOCl₃, WBr₃, WCl₆, WOCl₄, MoCl₅,MoOCl₄, WO₂, and H₂WO₄ can be given. Among these compounds, compounds ofW, Mo, Ti, or V, particularly a halide, an oxyhalide, or an alkoxyhalideare preferable from the viewpoint of polymerization activity.

The metallic compound co-catalyst component (β) is a compound having atleast one metal element-carbon atom bond or at least one metalelement-hydrogen bond of a metal belonging to the groups 1 to 2 and thegroups 12 to 14 of the Periodic Table. For example, an organic compoundof Al, Sn, Li, Na, Mg, Zn, Cd, and B can be given.

As specific examples, organoaluminum compounds such astrimethylaluminum, triisobutylaluminum, diethylaluminum monochloride,methylaluminum sesquichloride, and ethylaluminum dichloride; organotincompounds such as tetramethyltin, diethyldimethyltin, tetrabutyltin, andtetraphenyltin; organiolithium compounds such as n-butyllithium;organosodium compounds such as n-pentylsodium; organomagnesium compoundssuch as methylmagnesium iodide; organozinc compounds such asdiethylzinc; organocadmium compounds such as diethyl cadmium; andorganoboron compounds such as trimethylboron can be given. Of these,compounds of elements belonging to the group 13, particularlyorganoaluminum compounds of Al, are preferable.

It is possible to increase the metathesis polymerization activity byadding a third component in addition to the component (α) and thecomponent (β). Examples of the third component used include aliphatictertiary amines, aromatic tertiary amines, molecular oxygen, alcohols,ethers, peroxides, carboxylic acids, acid anhydrides, acid chlorides,esters, ketones, nitrogen-containing compounds, halogen-containingcompounds, and other Lewis acids.

The ratio of the component (α) to the component (β), in terms of molarratio of metals, is usually in a range of 1:1 to 1:100, and preferably1:2 to 1:10. The molar ratio of the component (α) to the third componentis usually in a range of 1:0.005 to 1:50, and preferably 1:1 to 1:10.

The amount of the polymerization catalyst used, in terms of molar ratioof the transition metals in the polymerization catalyst to the totalamount of monomers, is usually 1:100 to 1:2,000,000, preferably 1:1,000to 1:20,000, and more preferably 1:5,000 to 1:8,000. If the amount ofthe catalyst is too large, the catalyst removal after the polymerizationreaction will become difficult and there is a possibility that themolecular weight distribution may be broadened. If too small, sufficientpolymerization activity may not be obtained.

It is preferable to carry out in the ring-opening polymerization in anappropriate solvent, although a non-solvent reaction is possible. Thereare no specific limitations to the organic solvent used insofar as thesolvent can dissolve or disperse the polymer or hydrogenated polymer anddoes not affect the polymerization reaction and the hydrogenationreaction. A common industrially available solvent is preferable.

As specific examples of such an organic solvent, aliphatic hydrocarbonssuch as pentane, hexane, and heptane; alicyclic hydrocarbons such ascyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane,trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane,decahydronaphthalene, bicycloheptane, tricyclodecane, hexahydroindenecyclohexane, and cyclooctane; aromatic hydrocarbons such as benzene,toluene, and xylene; halogen-containing aliphatic hydrocarbons such asdichloromethane, chloroform, and 1,2-dichloroethane; halogen-containingaromatic hydrocarbons such as chlorobenzene and dichlorobenzene;nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene, andacetonitrile; ethers such as diethyl ether and tetrahydrofuran; and thelike can be given. These organic solvents may be used eitherindividually or in combinations of two or more.

Of these, common industrial solvents such as aromatic hydrocarbons,aliphatic hydrocarbons, alicyclic hydrocarbons, and ethers arepreferably used.

When the polymerization is carried out in an organic solvent, theconcentration of 2-norbornene or the monomer mixture consisting of2-norbornene and substituent-containing norbornene monomers ispreferably 1 to 50 wt %, more preferably 2 to 45 wt %, and particularlypreferably 3 to 40 wt %. If the concentration of 2-norbornene or themonomer mixture is less than 1 wt %, the productivity may be reduced; ifmore than 50 wt %, the solution viscosity after polymerization is toohigh, and there is a possibility that the subsequent hydrogenationreaction may become difficult.

It is preferable to add a molecular weight controlling agent to thering-opening polymerization reaction system. The molecular weight of thering-open polymer may be adjusted by adding a molecular weightcontrolling agent.

Any molecular weight controlling agent conventionally used may be usedwithout a particular limitation.

As examples, α-olefins such as 1-butene, 1-pentene, 1-hexene, and1-octene; styrenes such as styrene and vinyltoluene; ethers such asethyl vinyl ether, isobutyl vinyl ether, and allyl glycidyl ether;halogen-containing vinyl compounds such as allylchloride;oxygen-containing vinyl compounds such as glycidyl methacrylate;nitrogen-containing vinyl compounds such as acrylamide; nonconjugateddienes such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene,1,6-heptadiene, 2-methyl-1,4-pentadiene, and 2,5-dimethyl-1,5-hexadiene;conjugated dienes such as 1,3-butadiene, 2-methyl-1,3-butadiene,2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene can begiven. Of these, α-olefins are preferable due to their capability ofeasily adjusting the molecular weight.

The amount of the molecular weight controlling agent may be the amountby which the polymers with a desired molecular weight can be obtained.Such an amount, in terms of molar ratio of the molecular weightcontrolling agent to the total amount of all monomers used, may beusually 1:50 to 1:1,000,000, preferably 1:100 to 1:5,000, and morepreferably 1:300 to 1:3,000.

The polymerization reaction is initiated by mixing 2-norbornene or amonomer mixture of 2-norbornene and substituent-containing norbornenemonomers with a polymerization catalyst.

Although not particularly limited, the polymerization temperature isusually −20° C. to +100° C., preferably 10° C. to 80° C., and morepreferably 30° C. to 60° C. If the temperature of the polymerizationreaction is too low, the reaction rate may be reduced. When thepolymerization temperature is too high, there is a possibility that themolecular weight distribution may be broadened.

Although not particularly limited, the polymerization reaction time isusually from one minute to 100 hours.

The pressure conditions are also not particularly limited. Thepolymerization reaction is usually carried out under pressure of 0 to 1MPa.

After the reaction, the target 2-norbornene ring-open polymer or2-norbornene ring-open copolymer (hereinafter referred to from time totime collectively as “norbornene ring-open polymer”) may be isolated byan ordinary post treatment operation.

The resulting norbornene ring-open polymer is supplied to the nexthydrogenation reaction step.

The hydrogenation reaction may also be continuously performed by addinga hydrogenation catalyst to the ring-opening polymerization orring-opening copolymerization reaction solution without isolating thenorbornene ring-open polymer as described later.

(Hydrogenation Reaction)

The hydrogenation reaction of the norbornene ring-open polymer is areaction of adding hydrogen to the carbon-carbon double bonds in themain chain of the norbornene ring-open polymer. The hydrogenationreaction is carried out by adding a hydrogenation catalyst to a solutionof 2-norbornene ring-open (co)polymer in an inert solvent whilesupplying hydrogen to the reaction system.

Any hydrogenation catalyst commonly used for hydrogenating olefincompounds may be used without specific limitations. The catalyst may beeither a homogeneous catalyst or a heterogeneous catalyst. Aheterogeneous catalyst is preferred when removal of metals from theresulting polymer or the like is considered.

As homogeneous catalysts, a catalyst system consisting of a combinationof a transition metal compound and an alkali metal compound, forexample, cobalt acetate and triethylaluminum, nickel acetylacetonate andtriisobutylaluminum, titanocene dichloride and n-butyllithium,zirconocene dichloride and sec-butyllithium, and tetrabutoxy titanateand dimethyl magnesium; a noble metal complex catalyst such asdichloro-bis(triphenylphosphine)palladium, chlorohydridocarbonyltris(triphenylphosphine)ruthenium, andchlorotris(triphenylphosphine)rhodium; and the like can be given.

As heterogeneous catalysts, nickel, palladium, platinum, rhodium, andruthenium, or solid catalysts with these metals supported on a carriersuch as carbon, silica, diatomaceous earth, alumina, or titania, forexample, nickel on silica, nickel on diatomaceous earth, nickel onalumina, palladium on carbon, palladium on silica, palladium ondiatomaceous earth, and palladium on alumina can be given.

The amount of the catalyst used is usually 0.05 to 10 parts by weightfor 100 parts by weight of the norbornene ring-open polymer.

As the inert organic solvent used for the hydrogenation reaction, thesame organic solvents as previously mentioned in connection with thering-opening polymerization of 2-norbornene or the ring-openingcopolymerization of 2-norbornene and substituent-containing norbornenemonomers may be given.

The hydrogenation reaction temperature varies according to thehydrogenation catalyst used. The reaction temperature is usually from−20 to +300° C., preferably from 0 to +250° C., and more preferably from100 to 200° C. If the temperature of the hydrogenation reaction is toolow, the reaction rate may be small. When the hydrogenation reactiontemperature is too high, a side reaction may occur.

After the hydrogenation reaction, the reaction solution is filtered toremove the hydrogenation catalyst and volatile components such as asolvent are removed from the polymer solution after the filtration toobtain the target hydrogenated norbornene ring-open polymer (I) or (II).

Since the hydrogenated norbornene ring-open polymers (I) and (II) of thepresent invention have good solubility in organic solvents, the polymerafter hydrogenation may be sufficiently purified by removing residualcatalysts and the like.

As the method of removing the volatile components such as a solvent fromthe polymer solution after filtration, known methods such as acoagulation method, a direct drying method, and the like can be given.

A coagulation method is a method of mixing a polymer solution with apoor solvent for the polymer to precipitate the polymer. Examples of thepoor solvent used include polar solvents including alcohols such asethyl alcohol, n-propyl alcohol, and isopropyl alcohol; ketones such asacetone and methyl ethyl ketone; and esters such as ethyl acetate andbutyl acetate.

The component in the form of particles obtained by precipitation isdried by heating under vacuum, in nitrogen, or in the air to obtain dryparticles, or made into pellets by extruding from a melt extruder.

A direct dry technique is a method of removing solvents by heating thepolymer solution under reduced pressure. This method may be carried outusing a centrifugal thin-film continuous vaporization dryer, asurface-scraping heat-exchange continuous reactor dryer, ahigh-viscosity reactor, or the like. The degree of vacuum and thetemperature are not particularly limited and are suitably selectedaccording to the apparatus used.

The degree of hydrogenation of the main chain double bonds in thehydrogenated norbornene ring-open polymers (I) and (II) (hereinafterreferred to from time to time as “hydrogenated ring-open polymer of thepresent invention”) is 80% or more, preferably 90% or more, morepreferably 95% or more, still more preferably 99% or more, andparticularly preferably 99.9% or more. The degree of hydrogenation ofthe above range prevents resin burning when molding and suppressesgeneration of a die line particularly when a film is formed.

The degree of hydrogenation of the hydrogenated ring-open polymer of thepresent invention can be determined by ¹H-NMR spectrum measurement usingdeuteriochloroform as a solvent.

The hydrogenated norbornene ring-open polymer (I) has apolystyrene-reduced weight average molecular weight (Mw), measured bygel permeation chromatography (GPC) using 1,2,4-trichlorobenzene as aneluant, of 50,000 to 200,000, preferably 70,000 to 180,000, and morepreferably 80,000 to 150,000.

The hydrogenated norbornene ring-open polymer (II) has apolystyrene-reduced weight average molecular weight (Mw), measured bygel permeation chromatography (GPC) using 1,2,4-trichlorobenzene as aneluant, of preferably 50,000 to 200,000, more preferably 70,000 to180,000, and particularly preferably 80,000 to 150,000.

If the Mw is in this range, the hydrogenated ring-open polymer has goodsolubility in solvents and can be produced with excellent productivity,purified with ease, and molded with ease. The molded article has goodmechanical properties and heat resistance. If the Mw is too large, thepolymer solution has high viscosity and can be filtered only withdifficulty, resulting in impaired productivity. In addition, a hightemperature is required for the resin in order to increase the filmthickness precision when producing a film, resulting in a die line dueto burning of the resin. If the Mw is too small, mechanical propertiesand heat resistance of the molded article may decrease. In addition,because the hydrogenated ring-open polymer is crystalline, thehydrogenated polymer dissolves in solvents only with difficulty,resulting in poor productivity of the polymer and difficulty in polymerpurification.

If the Mw is in this range, the hydrogenated ring-open polymer exhibitsexcellent blister moldability and produces a molded article withexcellent strength. If the Mw is too large, blister moldability isimpaired. It is difficult to mold the resin by blister molding or, ifmolded by blister molding, the molded article may have some defects suchas an uneven or deflected thickness. On the other hand, if the Mw is toosmall, the blister molded article may have poor mechanical strength.

The upper limit of the molecular weight distribution (Mw/Mn) of thehydrogenated norbornene ring-open polymer (I) of the present inventionis 10.0, preferably 9.0, more preferably 8.5, and still more preferably8.0. The lower limit of (Mw/Mn) is 1.5, preferably 2.0, and morepreferably 2.5.

Although not particularly limited, the upper limit of the molecularweight distribution (Mw/Mn) of the hydrogenated norbornene ring-openpolymer (II) is preferably 10.0, more preferably 9.0, still morepreferably 8.5, and particularly preferably 8.0. Although there are noparticular limitations, the lower limit of (Mw/Mn) is preferably 1.5,more preferably 2.0, and still more preferably 2.5.

If the Mw/Mn is in this range, the hydrogenated ring-open polymerexhibits excellent blister moldability and produces a molded articlewith excellent strength and heat resistance. If the Mw/Mn is too narrow,the melting viscosity of the hydrogenated ring-open polymer delicatelychanges according to a change of temperature, resulting in impairedprocessability of the molded article such as a film and a sheet. Inaddition, if the resin is molded by blister molding, the molded articlemay have some defects such as an uneven or deflected thickness. On theother hand, if the Mw/Mn is too broad, the molded article may have poormechanical strength and decreased heat resistance.

The Mn is determined as a standard polystyrene-reduced value by gelpermeation chromatography (GPC) using 1,2,4-trichlorobenzene as aneluant.

The hydrogenated ring-open polymer of the present invention iscrystalline and, therefore, has a melting point (hereinafter referred tofrom time to time as “Tm”). The melting point of the hydrogenatedring-open polymer is 110 to 145° C., preferably 120 to 145° C., and morepreferably 130 to 145° C.

If the Tm is in the above range, the molded article has good heatresistance. The melting point in a range of 130 to 145° C. is preferabledue to capability of the resin to withstand steam sterilization whenproducing molded articles for medical or food use.

The melting point of the hydrogenated ring-open polymer is determinedaccording to JIS K7121 using a general differential scanningcalorimeter.

The melting point of the hydrogenated ring-open polymer varies accordingto the molecular weight, molecular weight distribution, isomerizationdegree, copolymerization ratio of 2-norbornene andsubstituent-containing norbornene monomers, and the like.

Since the hydrogenated ring-open polymer of the present invention has amelting point and, therefore, possesses a crystalline structure, thepolymer forms crystalline areas in the blister-molded article. Thecrystalline areas improve the mechanical properties such as tensilebreaking elongation and the like in combination with amorphous areas. Inspite of such characteristics, the molded article has good transparencybecause of the small size crystal.

The isomerization ratio of the hydrogenated ring-open polymer of thepresent invention is usually 0 to 40%, preferably 0 to 20%, morepreferably 1 to 10%, and still more preferably 1 to 5%. If theisomerization ratio is too high, the polymer may have reduced heatresistance. If the isomerization ratio is too low, on the other hand,the polymer has reduced solubility in solvents, resulting in poorproductivity of the polymer and difficulty in polymer purification. Inaddition, the molded article may have impaired transparency.

The isomerization ratio of the hydrogenated ring-open polymer of thepresent invention can be calculated using an equation, 33.0 ppm peakintegration value/(31.8 ppm peak integration value+33.0 ppm peakintegration value)×100, wherein the peak integration values aredetermined by ¹³C-NMR spectrum measurement using deuteriochloroform as asolvent.

The 31.8 ppm peak is a peak derived from cis-isomers of 2-norbornenerepeating units in the hydrogenated ring-open polymer and the 33.0 ppmpeak is a peak derived from trans-isomers of 2-norbornene repeatingunits in the hydrogenated ring-open polymer.

In order to produce a norbornene ring-open polymer having theisomerization ratio of the above range, the hydrogenation reactiontemperature of the norbornene ring-open polymer is preferably 100 to200° C., more preferably 120 to 170° C., and still more preferably 130to 160° C., and the amount of the hydrogenation catalyst shouldpreferably be 0.1 to 5 parts by weight, and more preferably 0.1 to 1part by weight for 100 parts by weight of the 2-norbornene ring-open(co)polymer. Such a hydrogenation reaction temperature and amount ofhydrogenation catalyst are preferable due to the excellently-balancedhydrogenation degree and heat resistance of the polymer.

The hydrogenated ring-open polymer exhibiting the above-describedcharacteristics is suitable as a resin material which provides excellentproperties such as steam barrier properties, heat resistance, oilresistance, mechanical properties, and processability demanded in recentyears in the fields of information processing, food industries, medicalsupplies, engineering works, and the like.

2) Resin Composition

The resin composition of the present invention comprises thehydrogenated ring-open polymer and an antioxidant.

The amount of antioxidant to be added is usually 0.01 to 1 part byweight, and preferably 0.05 to 0.5 parts by weight for 100 parts byweight of the hydrogenated ring-open polymer. If the amount ofantioxidant is too small, the molded article may be easily burnt(colored). On the other hand, if the amount if too large, the moldedarticle may be whitened or allow the antioxidant to elute therefrom.

Although there are no particular limitations, the molecular weight ofthe antioxidant used is preferably 700 or more. If the molecular weightof the antioxidant is too small, the molded article may allow theantioxidant to elute therefrom.

As specific examples of the antioxidant, phenolic antioxidants such asoctadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,tetrakis[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane,andpentaerythrityltetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate];phosphorus antioxidants such as triphenylphosphite,tris(cyclohexylphenyl)phosphite, and9,10-dihydro-9-oxa-10-phosphaphenanthrene; sulfur-containingantioxidants such as dimyristyl-3,3′-thiodipropionate,distearyl-3,3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate,and pentaerythritoltetrakis((3-laurylthiopropionate); and the like canbe given. These antioxidants may be used either individually or incombination of two or more. Among these, phenolic antioxidants arepreferable.

In addition to the hydrogenated ring-open polymer and the antioxidant,the resin composition of the present invention may include various otheradditives which are commonly used in synthetic resins to the extent thatthe object of the present invention is not inhibited.

Examples of the additives include rubber-like polymers and other resins,UV absorbers, weather-resistant stabilizers, antistatic agents, slippingagents, anticlouding agents, dyes, pigments, coloring agents, naturaloils, synthetic oils, plasticizers, organic or inorganic fillers,antibacterial agents, deodorants, and the like.

The rubber-like polymers are polymers having a glass transitiontemperature of 40° C. or less and include rubbers and thermoplasticelastomers. When the polymer has two or more glass transitiontemperatures such as in the case of a block copolymer, such a polymermay be used as the rubber-like polymer if the lowest glass transitiontemperature is not more than 40° C. Although the viscosity of therubber-like polymer may be suitably selected according to the purpose ofuse, the Mooney viscosity (ML₁₊₄, 100° C.) is usually 5 to 300.

As examples of the rubber-like polymer, an ethylene α-olefin rubber; anethylene-α-olefin polyene copolymer rubber; a copolymer of ethylene andunsaturated carboxylate such as ethylene methyl methacrylate andethylene butyl acrylate; a copolymer of ethylene and a fatty acid vinylester such as an ethylene-vinyl acetate copolymer; a polymer of alkylacrylate such as ethyl acrylate, butyl acrylate, hexyl acrylate,2-ethylhexyl acrylate, and lauryl acrylate; diene rubbers such aspolybutadiene, polyisoprene, a random copolymer of styrene and butadieneor isoprene, an acrylonitrile-butadiene copolymer, a butadiene isoprenecopolymer, a butadiene-alkyl (meth)acrylate copolymer, abutadiene-alkyl(meth)acrylate-acrylonitrile copolymer, and abutadiene-alkyl(meth)acrylate-acrylonitrile-styrene copolymer; abutylene-isoprene copolymer; block copolymers of aromatic vinylconjugated diene such as a styrene-butadiene block copolymer, ahydrogenated styrene-butadiene block copolymer, a hydrogenatedstyrene-butadiene random copolymer, a styrene-isoprene block copolymer,and a hydrogenated styrene-isoprene block copolymer; a low crystallinepolybutadiene resin, an ethylene-propylene elastomer, a styrene-graftedethylene-propylene elastomer, a thermoplastic polyester elastomer, anethylene ionomer resin, and the like can be given.

The amount of the rubber-like polymers is suitably selected according tothe purpose of use. When impact resistance and pliability are demanded,the amount of the rubber-like polymers is usually in a range from 0.01to 100 parts by weight, preferably from 0.1 to 70 parts by weight, andmore preferably from 1 to 50 parts by weight for 100 parts by weight ofthe hydrogenated ring-open polymer.

As examples of the other resins, an amorphous norbornene ring-openpolymer, an amorphous hydrogenated norbornene ring-open polymer, anamorphous norbornene addition polymer, a crystalline norbornenering-open polymer, a crystalline hydrogenated norbornene ring-openpolymer other than the hydrogenated ring-open polymer of the presentinvention, a crystalline norbornene addition polymer, a low densitypolyethylene, a high density polyethylene, a linear low densitypolyethylene, a super-low density polyethylene, an ethylene-ethylacrylate copolymer, an ethylene-vinyl acetate copolymer, polypropylene,polystyrene, hydrogenated polystyrene, polymethyl methacrylate,polyvinyl chloride, polyvinylidene chloride, polyphenylene sulfide,polyphenylene ether, polyamide, polyester, polycarbonate, cellulosetriacetate, polyether imide, polyimide, polyallylate, polysulfone,polyether sulfone, and the like can be given.

These resins may be used either individually or in combination of two ormore in any proportion not affecting the purpose of the presentinvention.

Examples of the UV absorbers and weather-resistant stabilizers includehindered amine compounds such as 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonate, and4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-1-{2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]ethyl}-2,2,6,6-tetramethylpiperidine;benzotriazole compounds such as2-(2-hydroxy-5-methylphenyl)benzotriazole,2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole,2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, and2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole; benzoate compounds suchas 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, andhexadecyl-3,5-di-t-butyl-4-hydroxybenzoate; and the like.

These UV absorbers and weather-resistant stabilizers may be used eitherindividually or in combination of two or more.

Although there are no specific limitations to the amount of the UVabsorbers and weather-resistant stabilizers, these additives are usuallyused in an amount of 0.001 to 5 parts by weight, and preferably 0.01 to2 parts by weight for 100 parts by weight of the hydrogenated ring-openpolymer.

As examples of the antistatic agent, long-chain alkyl alcohols such asstearyl alcohol and behenyl alcohol; sodium alkyl sulfonate and/orphosphonium salt of alkyl sulfonic acid; fatty acid esters such asglycerol ester of stearic acid; hydroxyamine compounds; amorphouscarbon, tin oxide powder, antimony-containing tin oxide powder; and thelike can be given. The antistatic agent is usually used in an amount of0.001 to 5 parts by weight for 100 parts by weight of the hydrogenatedring-open polymer.

As an example of the method for preparing the resin composition of thepresent invention, a method of melt-kneading the hydrogenated ring-openpolymer of the present invention together with the Antioxidant And otheroptional additives using a twin-screw kneader, for example, at 200 to400° C., and producing pellets, granules, or powder from the kneadedproduct can be given.

The resin composition obtained in this manner has excellentprocessability. The film thickness fluctuation, when a monolayer film isprepared from the hydrogenated ring-open polymer or the resincomposition of the present invention by a known T-die melt extruder, isusually not more than 10 μm, and preferably not more than 7 μm. In nocase is a die line not produced for a long time during a continuous filmforming operation. The period of time for which the film can be formedwithout producing a die line is usually 10 hours or more, and morepreferably 15 hours or more.

The term “die line” refers to a streak, observable with the naked eye,continuously generated along the direction of extrusion of the resin atthe position of the molded article corresponding to the specificposition of the die. More specifically, the die line is a streak formedon the surface of the molded article consisting of irregularities(concaves and convexes) with a height of about 0.3 μm to 100 μm. Smallerconcaves and convexes cannot be observed with the naked eye.

3) Resin Film or Sheet

The resin film or sheet of the present invention (hereinafter referredto from time to time as “resin film and the like of the presentinvention”) can be obtained by molding the hydrogenated ring-openpolymer or the resin composition of the present invention.

There are no specific limitations to the method of molding thehydrogenated ring-open polymer or the resin composition of the presentinvention. Either a heat-melting molding method or a solution castmethod may be used.

The heat-melting molding method is a method of fluidizing the moldingmaterial by heating at a temperature above Tm, but lower than thethermal cracking temperature of the polymer, and molding the fluidizedmaterial into a film or sheet.

The heat-melting molding method includes an extrusion molding method, acalender molding method, a compression molding method, an inflationmolding method, an injection molding method, a blow molding method, anextension molding method, and the like.

It is possible to apply the extension molding method to a film producedby the extrusion molding method, calender molding method, inflationmolding method, or the like.

The heating conditions and pressure conditions in the heat-meltingmolding method may be appropriately selected according to the type ofmolding machine and properties of the hydrogenated ring-open polymer. Atemperature in the range usually from Tm to (Tm+100° C.), and preferablyfrom (Tm+20° C.) to (Tm+50° C.) is applied under a pressure of usuallyfrom 0.5 to 100 MPa, and preferably from 1 to 50 MPa.

The reaction time is usually from about several seconds to several tensof minutes.

The hydrogenated ring-open polymer of the present invention has acomparatively high Tm and high heat resistance, but becomes fluid at atemperature between 200° C. and 400° C. by a remarkable reduction in theviscosity.

Although the reason is not clear, the polymer is thought to rapidlydecrease in viscosity at a temperature in the above range by forming aliquid crystal state due to the crystalline properties. Therefore, thehydrogenated ring-open polymer of the present invention flows well inspite of the high melting temperature and can be molded into a film or asheet in a short time.

On the other hand, the solution cast method is a method of dissolvingthe resin composition of the present invention in an organic solvent,casting the solution on a plane or a roll, and removing the solvent byheating to obtain a film and a sheet.

As the solvent used, the same solvents as previously mentioned inconnection with the ring-opening polymerization of 2-norbornene, thering-opening copolymerization of 2-norbornene and substituent-containingnorbornene monomers, and hydrogenation of the norbornene ring-openpolymer may be given.

The solution cast method is carried out at a temperature at which thesolvent volatilizes. The molding temperature is thus appropriatelydetermined according to the type of the solvent used.

The molded article may be annealed in order to increase crystallinity.

There are no specific limitations to the thickness of the resin film andthe like of the present invention. The thickness is usually 1 μm to 20mm, preferably 5 μm to 5 mm, and more preferably 10 μm to 2 mm. A filmis not distinguished from a sheet by any specific definition, althoughthese terms are sometimes distinguished according to the thickness, thenames (film or sheet) used according to the application and the practicein the industry.

Since the hydrogenated ring-open polymer molded into the film or thelike of the present invention has a melting point and, therefore,possesses a crystalline structure, the polymer forms crystalline areasin the molded film or sheet. The crystalline areas improve themechanical properties such as tensile breaking elongation and the likein combination with amorphous areas, and yet allows the film or thesheet to exhibit excellent transparency due to the small size of thecrystals.

In order to increase the mechanical strength and steam barrierproperties, the film or the sheet may be stretched to increase thecrystallinity. This is an operation of applying plastic deformation to asheet or film by stretching the length of the molded film or sheet 1.1to 10 times. The plastic deformation has an effect of orientingamorphous chains, not to mention crystalline chains, by internalfriction caused by stretching.

The resin film of the present invention may be a laminate of a layercontaining the hydrogenated ring-open polymer and a layer containingother polymers.

As the other polymers, rubber-like polymers and other resins may begiven. The same polymers and resins previously mentioned as those usedtogether with the hydrogenated ring-open polymer may be given asspecific examples of such other polymers.

Although the number of the layers to be laminated is usually two orthree, the film or the sheet may be a multilayer laminate consisting ofmore than three layers. The order of the types of polymers in layers ofthe three or more multilayer laminate may be determined according to thepurpose and application.

In addition, it is possible to dispose layers of the same polymerseparated by a layer of another polymer. For example, it is possible toform a three layer laminate having a layer containing polystyrenesandwiched between two layers containing the hydrogenated ring-openpolymer, or to form a four layer laminate having a layer containing ahydrogenated styrene-isoprene block copolymer disposed on either side ofthe three layer laminate.

As the laminating method, a method of pasting two layers by applying anadhesive between them, a method of bonding a monolayer or a multilayerfilm or sheet at a temperature above the melting point by heat or highfrequency, a method of preparing a dispersion or solution of thehydrogenated ring-open polymer or the other polymers in an organicsolvent, applying the dispersion or solution to the surface of the filmor sheet of the other polymers or the hydrogenated ring-open polymer,and drying the dispersion of the solution, and the like can be given.

A laminate may also be produced by co-extruding the hydrogenatedring-open polymer and the other polymers from an extruder.

The resin film and the like of the present invention have excellentsteam barrier properties, heat resistance, oil resistance, andmechanical properties such as tensile breaking elongation. The film andthe like have an advantage of a wide processing temperature range due tothe high thermal decomposition temperature.

The resin film and the like of the present invention have excellentmechanical properties. The tensile breaking elongation of the resin filmand the like of the present invention measured based on ISO 527 isusually 25% or more, and preferably 30% or more.

The resin film and the like of the present invention have excellentsteam barrier properties. The resin film or sheet of the presentinvention with a thickness of 100 μm has a moisture permeability(g/(m²·24 h)) measured based on JIS K7129 (Method A) of usually 0.5(g/(m²·24 h)) or less, and preferably 0.4 (g/(m²·24 h)) or less.

The resin film and the like of the present invention have excellent oilresistance. In a test comprising preparing a test specimen with adimension of 10 mm×100 mm×1 mm by heat-pressing the resin composition ofthe present invention, applying salad oil to the surface of the testspecimen, and securing the test specimen for one hour to a curvedaluminum jig made by cutting an elliptic cylinder with a height of 10 mmhaving an ellipse form side with a major axis of 200 mm and a minor axisof 80 mm into equal four divisions, the test specimen did not producecracks.

The resin film of the present invention which has these features can beused for a wide variety of applications in the fields of foodindustries, medical supplies, displays, energy, optical appliances,electric and electronic parts, telecommunications sector, vehicles,public welfare, civil engineering and construction, and the like.

The fields in which the resin film of the present invention isparticularly useful include the fields of food industries, medicalsupplies, energy, displays, and the like.

Applications in the fields of food industries include food packaging,such as a wrap film, a shrink film, and a film for blister packages ofprocessed foods such as ham, sausage, pouch-packed food, and frozenfood, dried food, specified health food, rice, confectionery, and meat,and the like.

In the medical field, the resin film of the present invention may beused as a medical bottle plug, an infusion bag, an intravenous drip bag,a film for a press through package (PTP), a film for blister packages,and the like.

In the energy fields, the resin film of the present invention may beused as an auxiliary component material of a solar energy powergeneration system, a fuel-cell peripheral component, analcohol-containing fuel system component, and a packing film of thesecomponents.

In the display field, the resin film of the present invention may beused as a barrier film, a phase difference film, a polarization film, anoptical diffusion sheet, a condensing sheet, and the like.

4) Molding Material and Molded Article

The molding material of the present invention is characterized bycontaining a hydrogenated norbornene ring-open polymer obtained byhydrogenating 80% or more of carbon-carbon double bonds of a ring-openpolymer which is obtained by ring-opening polymerization of 2-norborneneor a monomer mixture of 2-norbornene and a substituent-containingnorbornene monomer, the proportion of a repeating unit (A) derived fromthe 2-norbornene with respect to all repeating units being 90 to 100 wt% and the proportion of a repeating unit (B) derived from thesubstituent-containing norbornene monomer with respect to all repeatingunits being 0 to 10 wt %, and the hydrogenated norbornene ring-openpolymer having a melting point of 110 to 145° C., the amount of organicsubstances discharged from the molding material when heated at 80° C.for 60 minutes being not more than 1 ppm.

Specifically, this hydrogenated norbornene ring-open polymer used as themolding material of the present invention is the same as thehydrogenated norbornene ring-open polymer of the present inventiondescribed above, except that weight average molecular weight (Mw)determined by gel permeation chromatography (GPC) or the molecularweight distribution (Mw/Mn) of the hydrogenated norbornene ring-openpolymer is not particularly limited, when such a polymer is obtained byhydrogenating 80% or more of main-chain carbon-carbon double bonds of aring-open polymer which is obtained by ring-opening polymerization of2-norbornene (hydrogenated 2-norbornene ring-open polymer). The polymersmentioned above as preferable examples of the hydrogenated norbornenering-open polymer of the present invention are the preferablehydrogenated norbornene ring-open polymers used as the molding materialof the present invention.

The monomer mixture used for producing the hydrogenated norbornenering-open polymer used for the molding material of the present inventioncomprises usually 90 to 100 wt %, preferably 95 to 99 wt %, and morepreferably 97 to 99 wt % of 2-norbornene and usually 0 to 10 wt %,preferably 1 to 5 wt %, and more preferably 1 to 3 wt % ofsubstituent-containing norbornene monomers.

The proportion of the repeating unit (A) derived from 2-norbornene withrespect to all repeating units of the hydrogenated norbornene ring-openpolymer used for the molding material of the present invention isusually 90 to 100 wt %, preferably 95 to 99 wt %, and more preferably 97to 99 wt %, and the proportion of the repeating unit (B) derived fromthe substituent-containing norbornene monomer with respect to allrepeating units of the hydrogenated norbornene ring-open polymer is 0 to10 wt %, preferably 1 to 5 wt %, and more preferably 1 to 3 wt %.

If the proportion of the repeating units (B) is within the above range,the resin has excellent heat resistance and discharges only a very smallamount of organic substances, and the resulting molded article generatesresin powder (foreign matter) by friction and the like only withdifficulty. If the proportion of the repeating units (B) is too large,the resin may have impaired heat resistance and may discharge anincreased amount of organic substances, and the resulting molded articletends to generate foreign matter by friction and the like with ease. Ifthe proportion of the repeating units (B) is too small, the resultingmolded article tends to easily generate foreign matter by friction.

The molding material of the present invention comprises one or more ofthe above hydrogenated norbornene ring-open polymers and, to an extentnot affecting the object of the present invention, may optionallycontain additives such as an antioxidant (stabilizer), an UV absorber, aweather-resistant stabilizer, an antistatic agent, other polymers suchas a thermoplastic resin and a soft polymer, a lubricant, and the like.

The content of the hydrogenated norbornene ring-open polymer in themolding material of the present invention is usually 50 wt % or more,preferably 70 wt % or more, and more preferably 90 wt % or more. Whenthe content is in this range, heat resistance and other characteristicssuch as the properties of discharging a minimal amount of organiccompounds are not affected.

If an antioxidant is added, a molded article of which the mechanicalstrength is reduced only with difficulty can be obtained.

There are no specific limitations to the antioxidant. A phenol-basedantioxidant, a phosphorus-containing antioxidant, a sulfur-containingantioxidant, a sulfur-containing antioxidant, a lactone-containingantioxidant, and the like can be given as examples.

As the phenol-based antioxidant, known phenol-based antioxidants such asacrylate phenol compounds disclosed in JP-A-63-179953 and JP-A-1-168643such as 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate and2,4-di-t-amyl-6-(1-(3,5-di-t-amyl-2-hydroxyphenyl)ethyl)phenyl acrylate;alkyl-substituted phenol compounds such as2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol,octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,2,2′-methylene-bis(4-methyl-6-t-butylphenol),4,4′-butylidene-bis(6-t-butyl-m-cresol),4,4′-thio-bis(3-methyl-6-t-butylphenol),bis(3-cyclohexyl-2-hydroxy-5-methylphenyl)methane,3,9-bis(2-(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane,1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane,1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene,tetrakis(methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenylpropionate)methane)[e.g.pentaerythrimethyltetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate)],triethylene glycolbis(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate), and tocophenol;

triazine group-containing phenol compounds such as6-(4-hydroxy-3,5-di-t-butylanilino)-2,4-bisoctylthio-1,3,5-triazine,6-(4-hydroxy-3,5-dimethylanilino)-2,4-bisoctylthio-1,3,5-triazine,6-(4-hydroxy-3-methyl-5-t-butylanilino)-2,4-bisoctylthio-1,3,5-triazine,and 2-octylthio-4,6-bis-(3,5-di-t-butyl-4-oxyanilino)-1,3,5-triazine;and the like can be given.

As the phosphorous-containing antioxidant, known phosphorous-containingantioxidants including mono-phosphite compounds such as triphenylphosphite, diphenylisodecyl phosphite, phenyldiisodecyl phosphite,tris(nonylphenyl)phosphite, tris(dinonylphenyl) phosphite,tris(2,4-di-t-butylphenyl)phosphite,tris(2-t-butyl-4-methylphenyl)phosphite,tris(cyclohexylphenyl)phosphite,2,2-methylene-bis(4,6-di-t-butylphenyl)octylphosphite,9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,and 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene;

diphosphite compounds such as4,4′-butylidene-bis(3-methyl-6-t-butylphenyl-di-tridecylphosphite),4,4′-isopropylidene-bis(phenyl-di-alkyl(C₁₂ to C₁₅)phosphite),4,4′-isopropylidene-bis(diphenyl-mono-alkyl(C₁₂ to C₁₅) phosphite),1,1,3-tris(2-methyl-4-di-tridecylphosphite-5-t-butylphenyl)butane,tetrakis(2,4-di-t-butylphenyl)-4,4′-biphenylenediphosphite, cyclicneopentan-tetra-yl-bis(iso-decylphosphite),cyclicneopentan-tetra-yl-bis(nonylphenylphosphite),cyclicneopentan-tetra-yl-bis(2,4-di-t-butylphenylphosphite),cyclicneopentan-tetra-yl-bis(2,4-dimethylphenylphosphite), cyclicneopentan-tetra-yl-bis(2,6-di-t-butylphenylphosphite); and the like canbe given.

Examples of sulfur-containing antioxidants include dilauryl3,3-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl3,3-thiodipropionate, laurylstearyl 3,3-thiodipropionate,pentaerythritoltetrakis(β-laurylthiopropionate),3,9-bis(2-dodecylthioethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane, and thelike.

Although any compounds containing a lactone structure may be used as alactone-based antioxidant without particular limitation, an aromaticlactone compound is preferable, and a compound having a benzofuranoneskeleton is more preferable, with 3-arylbenzofuran-2-one having an arylgroup as a substituent on the side chain of the furan ring being evenmore preferable. As an specific example,5,7-di-t-butyl-3-(3,4-di-methylphenyl)-3H-benzofuran-2-one can be given.

Among these antioxidants, an alkyl-substituted phenolic antioxidant isparticularly preferable in the present invention. In order to preventvolatilization, an antioxidant with a vapor pressure of not higher than10⁻⁶ Pa at 20° C. is preferable.

The antioxidants may be used either individually or in combination oftwo or more.

The amount of the antioxidant used in the present invention may beappropriately determined in a range not impairing the effect of thepresent invention. Such an amount is usually from 0.001 to 5 parts byweight, and preferably from 0.01 to 1 part by weight for 100 parts byweight of the hydrogenated ring-open polymer.

Examples of the UV absorbers and weather-resistant stabilizers includehindered amine compounds such as 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonate, and4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-1-{2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]ethyl}-2,2,6,6-tetramethylpiperidine;benzotriazole compounds such as 2-(2-hydroxy-5-methylphenyl)benzotriazole,2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole,2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, and2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole; benzoate compounds suchas 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, andhexadecyl-3,5-di-t-butyl-4-hydroxybenzoate; and the like. These UVabsorbers and weather-resistant stabilizers may be used eitherindividually or in combination of two or more.

The amount of the UV absorbers and weather-resistant stabilizers isusually from 0.001 to 5 parts by weight, and preferably 0.01 to 2 partsby weight for 100 parts by weight of the hydrogenated ring-open polymer.

The antistatic agent is added to provide an antistatic effect.

As examples of the antistatic agent, long-chain alkyl alcohols such asstearyl alcohol and behenyl alcohol; sodium alkyl sulfonate and/orphosphonium salt of alkyl sulfonic acid; fatty acid esters such asglycerol ester of stearic acid; hydroxyamine compounds; amorphouscarbon, tin oxide powder, antimony-containing tin oxide powder; and thelike can be given.

The antistatic agent is usually used in an amount of 0.001 to 50 partsby weight for 100 parts by weight of the hydrogenated ring-open polymer.

Other polymers such as a thermoplastic resin and a soft polymer areadded in order to improve mechanical properties and moldability.

As examples of the thermoplastic resin, polyolefins such as low densitypolyethylene, high density polyethylene, linear low densitypolyethylene, super-low density polyethylene, polypropylene, polybutene,and polypentene; polyesters such as polyethyleneterephthalate andpolybuthyleneterephthalate; polyamides such as nylon 6 and nylon 6,6;ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer,polystyrene, polyphenylene sulfide, polyphenylene ether, polyamide,polyester, polycarbonate, and the like can be given.

As the soft polymer, a polymer of which at least one glass transitiontemperature (Tg) is 40° C. or less may be used without particularlimitation. For example, random or block copolymers of an aromatic vinylmonomer and a conjugated diene type monomer and hydrogenated productthereof such as a styrene-butadiene block copolymer, astyrene-butadiene-styrene block copolymer, a styrene-isoprene blockcopolymer, a styrene-isoprene-styrene block copolymer, and astyrene-butadiene random copolymer; polyisopropyrene rubber; polyolefinrubbers such as an ethylene-propylene copolymer, an ethylene-α-olefincopolymer, and a propylene-α-olefin copolymer; diene copolymers such asan ethylene-propylene-diene copolymer, an α-olefin-diene copolymer, adiene copolymer, an isobutylene-isoprene copolymer, and anisobutylene-diene copolymer; norbornene-based rubbers such as acopolymer of a norbornene monomer and ethylene, or an α-olefin, aternary copolymer of a norbornene monomer and ethylene or an α-olefin,and a ring-open polymer of a norbornene monomer; and the like can begiven.

A lubricant is added in order to improve moldability.

As a lubricant, a partial ester of a polyhydric alcohol, a full ester ofa polyhydric alcohol (a compound in which 95% or more of alcoholichydroxyl groups of polyhydric alcohol is esterified), a saturated higheralcohol, a partial ether of a polyhydric alcohol, and the like can begiven. Of these, the full ester of polyhydric alcohol is preferable,with a full ester of a polyhydric alcohol and an OH group-containingsaturated higher fatty acid and a saturated higher fatty acid beingparticularly preferable. In order to prevent volatilization duringmolding, a lubricant with a vapor pressure of not higher than 10⁻⁶ Pa at20° C. is preferable.

Although the amount of lubricant may be appropriately selected accordingto the purpose of use, the lubricant is usually used in an amount of0.001 to 10 parts by weight, and preferably 0.01 to 5 parts by weightfor 100 parts by weight of the hydrogenated ring-open polymer.

The molding material of the present invention may further contain otheradditives such as a light stabilizer, a near-infrared absorbent, acoloring agent such as a dye and a pigment, a lubricant, a plasticizer,an anti blocking agent, a fluorescent bleach, a deodorant, an organic orinorganic filler, a crosslinking agent, a vulcanizing agent, a wax, andthe like.

The amount of these other additives may be arbitrarily determined to theextent that the object of the present invention is not impaired.

When the molding material of the present invention is a resincomposition, there are no specific limitations to the method forpreparing the resin composition. A method of melting and mixing thehydrogenated ring-open polymer and the additives using a kneader such asa mono-axial extruder, biaxial extruder, a roller, a Banbury mixer, andthe like may be given.

The amount of organic substances discharged from the molding material ofthe present invention when heated at 80° C. for 60 minutes is not morethan 1 ppm, preferably not more than 150 ppb, more preferably not morethan 50 ppb, more preferably not more than 20 ppb, and particularlypreferably not more than 10 ppb. If the amount of organic substancesdischarged from the molding material is in the above range, there willbe no possibility that the resulting molded articles discharge organicsubstances. A molding material providing this property is preferableparticularly when the molded article is a wafer carrier forsemiconductor production, since the wafer is not polluted with theorganic substances.

The amount of organic substances discharged may be determined by, forexample, a method of washing 5 g of the molding material sample with alarge amount of ultra pure water in a clean room (class 1000), placingthe sample in a glass sample container completely free from moisture andorganic substances adhering to the surface, heating the sample containerat 80° C. for 60 minutes, and measuring gases discharged from the samplecontainer by a heat desorption gas chromatography mass spectrometer(e.g. TDS-GC-MS manufactured by Agilent Technologies).

In order to obtain the molding material discharging not more than 1 ppmof organic substances when heated at 80° C. for 60 minutes, it is onlynecessary to remove as many volatile components such as solvents aspossible from the hydrogenated ring-open polymer after filtration.

As the method of removing the solvents and the like, a coagulationmethod, a direct drying method, and the like can be given.

The coagulation method is a method of removing solvents by mixing thepolymer solution with a poor solvent for the polymer to precipitate thepolymer and separating the coagulated components from the liquid.

Examples of the poor solvent used include polar solvents such asalcohols such as, for example, methyl alcohol, ethyl alcohol, n-propylalcohol, and isopropyl alcohol; ketones such as acetone and methyl ethylketone; and esters such as ethyl acetate and butyl acetate.

After separating the coagulated components from the liquid, it ispreferable that the resulting small polymer crumb be heated and dried toremove the solvent.

A direct drying technique is a method of removing solvents by heatingthe polymer solution under reduced pressure. This method may be carriedout using a commonly known apparatus, for example, a thin film driersuch as a centrifugal thin-film continuous vaporization dryer, asurface-scraping heat-exchange continuous reactor dryer, ahigh-viscosity reactor, or the like. The degree of vacuum and thetemperature are not particularly limited and are suitably selectedaccording to the apparatus used.

After removing the solvent by the coagulation method or the directdrying technique, it is preferable to further heat and dry under reducedpressure of usually 10 kPa or less, and preferably 3 kPa or less at atemperature of usually 200° C. or more, preferably 220° C. or more, andmore preferably 240° C. or more. These drying conditions allow almost nounreacted monomers and solvents to remain in the polymer and thus reduceorganic substances volatilizing from the formed articles.

It is preferable that the content of transition metals of the moldingmaterial of the present invention be not more than 1 ppm. If the contentof transition metals is not more than 1 ppm, there is no possibility ofelusion of metals from the molded articles. When the molded article is awafer carrier for semiconductor production, this feature of the presentinvention is particularly preferable. Since metals are not eluted bywashing with an acid or alkali, the wafer carrier is not polluted withthe eluted metals.

There are no particular limitations to the type of transition metals.These metals are mixed in from the polymerization catalyst,hydrogenation catalyst, environmental foreign matter, and manufacturingequipment, and mainly originate from the polymerization catalyst andhydrogenation catalyst used in the process.

The content of transition metals in the molding material may bedetermined by inductively coupled plasma optical emission spectrometryusing, for example, IRIS Advantage/SSEA, manufactured by NipponJarrell-Ash Co. Ltd.

As a method for obtaining the molding material with a transition metalcontent of not more than 1 ppm, a method of hydrogenating the ring-openpolymer using a heterogeneous catalyst and filtering the resultinghydrogenation reaction solution, a method of treating the solution ofthe hydrogenated ring-opening polymer or the solution of the resincomposition obtained by adding the additives to the hydrogenatedring-opening polymer (hereinafter referred to from time to time as“resin solution”) with an adsorbent to adsorb the metal atoms, a methodof repeatedly washing the resin solution with an acidic solution andpure water in turn, and the like can be given. Among these methods, themethod of hydrogenation using a heterogeneous catalyst and filtering theresulting hydrogenation reaction solution is preferable.

As the method for hydrogenation using a heterogeneous catalyst andfiltering the resulting hydrogenation reaction solution, a method ofhydrogenating using a heterogeneous catalyst, followed by (i) filteringthe hydrogenation reaction solution through a filter having a chargecapturing function or (ii) filtering the hydrogenation reaction solutionat least twice using a mechanical filter having pores with a diameter of0.5 μm or less, preferably 0.3 μm or less, may be given.

Among these, the method (i) is preferred because the method (i) has highcapability of removing fine foreign matter which may pass through poresof a mechanical filter and preventing regeneration of foreign matter dueto re-coagulation after filtration.

The filter having a charge capturing function is a filter which cancapture and remove electrically-charged foreign matter. As the filterhaving a charge capturing function, a filter of which the filteringmaterial is charged, for example, a zeta potential filter which iscontrolled by a zeta potential, can be given.

As the zeta potential filter, a filter made from a material providedwith a cationic charge modifier and the like may be given.

As examples of the cationic charge modifier, a cellulosefiber/silica/cationic charge modifier (polyamine epichlorohydrin resin,aliphatic polyamine, etc.) described in Published Japanese Translationof PCT Application 4-504379, etc., melamine formaldehyde cationiccolloid, inorganic cationic colloidal silica, and the like may be given.

In addition, a product commercially available from CUNO K.K. under thetrademark of “Zeta Plus” may be used as a filter made from a materialprovided with a cationic charge modifier.

Furthermore, in order to increase the processing capacity, a mechanicalfilter may be used in combination with the filter having a chargecapturing function. From the viewpoint of processing efficiency, it ispreferable that the hydrogenation reaction solution be first filtered bya mechanical filtration, and then by the charge capture function.

Any mechanical filters which are not damaged by a solvent may be usedwithout particular limitation. For example, fiber filters or membranefilters made from polypropylene, polyethylene, or PTFE; fiber filtersmade from cellulose; glass fiber filters; filters made from an inorganicsubstance such as diatomaceous earth; and filters made from a metalfiber can be given.

Although not particularly limited, the pore diameter of the mechanicalfilters is usually 10 μm or less, preferably 5 μm or less, and morepreferably 1 μm or less. Either one mechanical filter or a combinationof two or more mechanical filters may be used.

The molding material of the present invention also exhibits excellentheat resistance. The heat resistance of the molding material of thepresent invention may be confirmed by, for example, allowing a wafercarrier for semiconductor production produced from the molding materialto stand at a temperature of 105° C. for 30 minutes and observingwhether or not the wafer carrier is deformed. No deformation will befound in the wafer carrier produced from the molding material of thepresent invention.

For ease of handling during a molding operation, the molding material ofthe present invention is processed into grains the size of rice calledpellets.

The molded article according to the present invention is obtained byforming the molding material of the present invention.

There are no specific limitations to the shape and size of the moldedarticle of the present invention. The molded article of the presentinvention includes a product of which a part is molded from the moldingmaterial of the present invention.

The molded article of the present invention can be produced by a knownmolding method using the molding material of the present invention. Asthe molding method, injection molding, calender molding, inflationmolding, extrusion blow molding, injection blow molding, multilayer blowmolding, connection blow molding, double wall blow molding, stretch blowmolding, vacuum molding, rotational molding, press molding, meltextrusion molding, and the like can be given. Among these methods,injection molding is preferable from the viewpoint of mass production.

A known injection molding machine may be used for injection molding.

The resin temperature (cylinder temperature) is usually from (Tm+5° C.)to (Tm+200° C.), and preferably from (Tm+20° C.) to (Tm+150° C.).

The cylinder residence time of the molding material of the presentinvention is usually within one hour, preferably within 30 minutes, andmore preferably within 10 minutes. When the molding material isinjection-molded under these conditions, the thermal decomposition(degradation) of the resin is prevented and generation of low molecularweight organic compounds is controlled.

When a certain period of time is required before molding the moldingmaterial after preparation, the prepared molding material is preferablystored in a sealed container, for example, a stainless container.

The molded article obtained in this manner produces foreign matter suchas resin powder by friction or the like only with difficulty.

The difficulty in producing foreign matter from the molded article canbe confirmed as follows, for example. First, in a clean room (class1000), an 8-inch new bear silicon wafer purchased in a state packed in apolypropylene wafer shipper is immersed in a 4.5 wt % solution ofhydrofluoric acid at 25° C. for one minute to remove a thin siliconoxide film. Next, the silicon wafer is immersed in a 50:1 (volume ratio)mixed solution of 98% concentrated sulfuric acid and 30% aqueoussolution of hydrogen peroxide at 110° C. for 10 minutes, then inconcentrated sulfuric acid at 65° C. for 10 minutes to remove organicsubstances. Next, after washing away acids with a large amount ofultra-pure water and completely removing the water by a centrifugalseparator, the number of foreign matter particles on the dried wafer iscounted using a foreign matter detector (for example, Surfscan SP1manufactured by KLA-Tencor corp.). After the wafer is inserted in andremoved from the molded wafer carrier 50 times, the number of foreignmatter particles on the wafer is counted again. The increase in thenumber of foreign matter particles in the test is usually 250 or less,preferably 230 or less, and more preferably 200 or less.

Since the molded article of the present invention has excellent heatresistance, discharges only a small amount of organic substances, andgenerates only a small amount of foreign matter, the molded article canbe suitably used as a material for fabricating electron processinginstruments. More particularly, such electron processing instrumentsinclude (A) instruments coming in contact with electronic parts such assemiconductors such ICs and LSIs, hybrid ICs liquid crystal displayelements, and light emitting diodes, (B) instruments coming in contactwith intermediate materials such as a wafer, a liquid crystal substrate,and a product obtained by laminating a transparent electrode layer, aprotective layer, etc. with the wafer or liquid crystal substrate, and(C) instruments coming in contact with a process solution used fortreating an intermediate material in the manufacturing process ofelectronic parts such as a chemical solution or ultra-pure water.

As (A) an instrument coming in contact with electronic parts and (B) aninstrument coming in contact with an intermediate material formanufacturing electronic parts, containers for processing ortransporting such as a tank, a tray, a carrier, a case, or a shipper;protective materials such as a carrier tape and a separation film; andthe like can be given. As the instruments (C) coming in contact with aprocess solution, piping instruments such as a pipe, a tube, a valve, aflowmeter, a filter, and a pump; fluid containers such as a samplingcontainer, a bottle, an ampoule, and a bag; and the like can be given.

Among these, the wafer carrier for semiconductor production isparticularly preferable. Since the surface of the wafer carrier forsemiconductor production of the present invention is damaged or hasforeign matter attached thereto only with difficulty during storage andtransportation, electronic parts and the like with high accuracy can beobtained by using the wafer carrier for semiconductor production of thepresent invention.

The molded article of the present invention may also be used as opticalrecording media such as an optical disc (e.g. a CD, a CD-ROM, a laserdisc, a digital videodisc, etc.), an optical card, and an optical tape;an optical lens, a prism, a beam splitter, a lens prism, an opticalmirror, an optical fiber, an LED sealing material, a substrate forliquid crystal display, a film for liquid crystal display, a lightguideplate for liquid crystal display, an optical film, a packing containerfor food, a packing container medical supplies, and the like.

The wafer carrier for semiconductor production of the present invention(hereinafter may be referred to from time to time as “carrier”) musthave a structure enabling the wafers to be held, removed, and insertedwithout causing them to come in contact with each other, and to besubjected to heat treatment or chemical treatment by dipping or thelike. Specifically, the wafers must be stored with planes held inparallel without coming into contact with each other and each wafer mustbe removed or inserted in the direction parallel to the plane.

Specifically, the wafers can be stored in a state in which a wafer and aspace are alternately arranged up in layers so that the wafers are heldin a framework provided with grooves or projections immovable in anydirection except for the extraction direction. In addition, in order toensure efficient and uniform heat treatment and dipping in chemicals,the wafer carrier has an inlet port for allowing a liquid or the like toflow into the spaces between the wafers from a direction other than thewafer extracting direction.

Specific examples of such carriers include those described inJP-A-2-63112, JP-A-2-143545, JP-A-2-161745, JP-A-3-95954, the carrierdescribed in FIG. 1, and those specified in the SEMI specification.

5) Multilayer Laminate

The multilayer laminate of the present invention is a laminate havingtwo or more resin layers. At least one layer is a layer of ahydrogenated norbornene ring-open polymer obtained by hydrogenating 80%or more of carbon-carbon double bonds of a ring-open polymer which isobtained by ring-opening polymerization of 2-norbornene or a monomermixture of 2-norbornene and a substituent-containing norbornene monomer.The proportion of the repeating unit (A) derived from the 2-norbornenewith respect to all repeating units is 90 to 100 wt % and the proportionof the repeating unit (B) derived from the substituent-containingnorbornene monomer with respect to all repeating units is 0 to 10 wt %,and the hydrogenated norbornene ring-open polymer has a melting point of110 to 145° C.

Specifically, the hydrogenated norbornene ring-open polymer used as themultilayer laminate of the present invention is the same as thehydrogenated norbornene ring-open polymer of the present inventiondescribed above, except that weight average molecular weight (Mw)determined by gel permeation chromatography (GPC) or the molecularweight distribution (Mw/Mn) of hydrogenated norbornene ring-open polymeris not particularly limited if such a polymer is obtained byhydrogenating 80% or more of main-chain carbon-carbon double bonds of aring-open polymer which is obtained by ring-opening polymerization of2-norbornene (hydrogenated 2-norbornene ring-open polymer). The polymersmentioned above as preferable examples of the hydrogenated norbornenering-open polymer of the present invention are the preferablehydrogenated norbornene ring-open polymers used as the multilayerlaminate of the present invention.

The monomer mixture used for producing the hydrogenated norbornenering-open polymer used for the multilayer laminate of the presentinvention comprises usually 90 to 100 wt %, preferably 95 to 99 wt %,and more preferably 97 to 99 wt % of 2-norbornene and usually 0 to 10 wt%, preferably 1 to 5 wt %, and more preferably 1 to 3 wt % ofsubstituent-containing norbornene monomers.

The proportion of the repeating unit (A) derived from 2-norbornene withrespect to all repeating units of the hydrogenated norbornene ring-openpolymer used for the multilayer laminate of the present invention isusually 90 to 100 wt %, preferably 95 to 99 wt %, and more preferably 97to 99 wt %, and the proportion of the repeating unit (B) derived fromthe substituent-containing norbornene monomer with respect to allrepeating units of the hydrogenated norbornene ring-open polymer is 0 to10 wt %, preferably 1 to 5 wt %, and more preferably 1 to 3 wt %.

Various additives may be added to the hydrogenated norbornene ring-openpolymer used for the multilayer laminate of the present inventionaccording to the purpose of application. Examples of the additivesinclude antioxidants, rubber-like polymers and other resins, UVabsorbers, weather-resistant stabilizers, antistatic agents, slippingagents, anticlouding agents, dyes, pigments, coloring agents, naturaloils, synthetic oils, plasticizers, organic or inorganic fillers,antibacterial agents, deodorants, and the like.

An antioxidant having a molecular weight of 700 or more is preferablyused. If the molecular weight of the antioxidant is too small, themolded article may allow the antioxidant to elute therefrom.

As specific examples of the antioxidant, phenolic antioxidants such asoctadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,tetrakis[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane,and pentaerythrityltetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]; phosphorusantioxidants such as triphenylphosphite,tris(cyclohexylphenyl)phosphite, and9,10-dihydro-9-oxa-10-phosphaphenanthrene; sulfur-containingantioxidants such as dimyristyl-3,3′-thiodipropionate,distearyl-3,3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate,and pentaerythritoltetrakis(β-laurylthiopropionate); and the like can begiven. These antioxidants may be used either individually or incombination of two or more. Among these, phenolic antioxidants arepreferable.

The amount of the antioxidant to be added is usually 0.01 to 1 part byweight, and preferably 0.05 to 0.5 parts by weight for 100 parts byweight of the hydrogenated norbornene ring-open polymer. If the amountof the antioxidant is too small, the molded article may be burnt(colored) with ease. On the other hand, if the amount is too large, themolded article may be whitened or allow the antioxidant to elutetherefrom.

The rubber-like polymers are polymers having a glass transitiontemperature of 40° C. or less and include rubbers and thermoplasticelastomers. When the polymer has two or more glass transitiontemperatures as in the case of a block copolymer, such a polymer may beused as the rubber-like polymer if the lowest glass transitiontemperature is not more than 40° C. Although the viscosity of therubber-like polymer may be suitably selected according to the purpose ofuse, the Mooney viscosity (ML₁₊₄, 100° C.) is usually 5 to 300.

As examples of the rubber-like polymer, an ethylene-α-olefin rubber; anethylene-α-olefin polyene copolymer rubber; a copolymer of ethylene andunsaturated carboxylate such as ethylene-methyl methacrylate andethylene-butyl acrylate; a copolymer of ethylene and a fatty acid vinylester such as an ethylene-vinyl acetate copolymer; a polymer of alkylacrylate such as ethyl acrylate, butyl acrylate, hexyl acrylate,2-ethylhexyl acrylate, and lauryl acrylate; diene rubbers such aspolybutadiene, polyisoprene, a random copolymer of styrene and butadieneor isoprene, an acrylonitrile butadiene copolymer, a butadiene isoprenecopolymer, a butadiene-alkyl(meth)acrylate copolymer, abutadiene-alkyl(meth)acrylate-acrylonitrile copolymer, and abutadiene-alkyl(meth)acrylate-acrylonitrile-styrene copolymer; abutylene-isoprene copolymer; block copolymers of aromatic vinylconjugated diene such as a styrene-butadiene block copolymer, ahydrogenated styrene-butadiene block copolymer, a hydrogenatedstyrene-butadiene random copolymer, a styrene-isoprene block copolymer,and a hydrogenated styrene-isoprene block copolymer; a low crystallinepolybutadiene resin, an ethylene-propylene elastomer, a styrene-graftedethylene-propylene elastomer, a thermoplastic polyester elastomer, anethylene ionomer resin, and the like can be given.

The amount of the rubber-like polymers is suitably selected according tothe purpose of use. When impact resistance and pliability are demanded,the amount of the rubber-like polymers is usually in a range from 0.01to 100 parts by weight, preferably from 0.1 to 70 parts by weight, andmore preferably from 1 to 50 parts by weight for 100 parts by weight ofthe hydrogenated norbornene ring-open polymer.

As examples of the other resins, an amorphous norbornene ring-openpolymer, an amorphous hydrogenated norbornene ring-open polymer, acrystalline norbornene addition polymer, an amorphous norborneneaddition polymer, a low density polyethylene, a high densitypolyethylene, a linear low density polyethylene, a super-low densitypolyethylene, an ethylene-ethyl acrylate copolymer, an ethylene-vinylacetate copolymer, polypropylene, polystyrene, hydrogenationpolystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinylidenechloride, polyphenylene sulfide, polyphenylene ether, polyamide,polyester, polycarbonate, cellulose triacetate, polyether imide,polyimide, polyallylate, polysulfone, polyether sulfone, and the likecan be given. These resins may be used either individually or incombination of two or more in any proportion not affecting the purposeof the present invention.

Examples of the UV absorbers and the weather-resistant stabilizersinclude hindered amine compounds such as 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonate, and4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-1-{2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]ethyl}-2,2,6,6-tetramethylpiperidine;benzotriazole compounds such as2-(2-hydroxy-5-methylphenyl)benzotriazole,2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole,2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, and2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole; benzoate compounds suchas 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, andhexadecyl-3,5-di-t-butyl-4-hydroxybenzoate; and the like. These UVabsorbers and the weather-resistant stabilizers may be used eitherindividually or in combination of two or more. The amount of the UVabsorbers and the weather-resistant stabilizers is usually from 0.001 to5 parts by weight, and preferably 0.01 to 2 parts by weight for 100parts by weight of the hydrogenated norbornene ring-open polymer.

As examples of the antistatic agent, long-chain alkyl alcohols such asstearyl alcohol and behenyl alcohol; sodium alkylsulfonate and/orphosphonium salt of alkylsulfonic acid; fatty acid esters such asglycerol ester of stearic acid; hydroxyamine compounds; amorphouscarbon, tin oxide powder, antimony-containing tin oxide powder; and thelike can be given. The antistatic agent is usually used in an amount of0.001 to 5 parts by weight for 100 parts by weight of the hydrogenatednorbornene ring-open polymer.

There are no particular limitations to the multilayer laminate of thepresent invention insofar as the multilayer laminate has two or moreresin layers of which at least one layer is a layer containing thehydrogenated ring-open polymer of the present invention. There are alsono particular limitations to the other layers (hereinafter may bereferred to from time to time as a “synthetic resin layer”).

The content of the hydrogenated norbornene ring-open polymer in thelayer which contains the hydrogenated norbornene ring-open polymer inthe multilayer laminate of the present invention is usually 50 to 100 wt%, preferably 70 to 100 wt %, and more preferably 90 to 100 wt %. Whenthe content is in this range, the characteristics possessed by thehydrogenated norbornene ring-open polymer such as steam barrierproperties are not affected.

Although there are no specific limitations, the thickness of the layercontaining the hydrogenated norbornene ring-open polymer is usually 1 to900 μm, preferably 10 to 400 μm, and more preferably 20 to 200 μm. Thisthickness range is preferable because the characteristics possessed bythe hydrogenated norbornene ring-open polymer such as steam barrierproperties are not affected.

When the multilayer laminate of the present invention is used formedical application or as a food packing material, it is preferable thatat least one of the synthetic resin layers is a layer containing a gasbarrier resin.

A multilayer laminate with excellent steam barrier properties, as wellas excellent gas barrier properties, can be obtained by using the layercontaining a gas barrier resin as the synthetic resin layer.

Since oxygen is the main gas that causes a problem of deterioration ofthe content and change of the composition, a resin with low oxygenpermeability is preferable as the gas barrier resin.

The gas barrier resin has oxygen permeability, when measured as a filmwith a thickness of 20 μm at 23° C. and 0% RH, of preferably not morethan 100 cm³·m⁻²·day⁻¹·atm⁻¹, more preferably not more than 50cm³·m⁻²·day⁻¹·atm⁻¹, still more preferably not more than 10cm³·m⁻²·day⁻¹·atm⁻¹, and particularly preferably not more than 1cm³·m²·day⁻¹·atm⁻¹.

As the gas barrier resin, a general purpose resin in the field ofpacking material and the like can be used. For example, anethylene-vinyl alcohol copolymer (EVOH), a vinylidene-chloride polymer(PVDC), polyesters with barrier properties such as apolyethylene-isophthalate copolymer, MXD6 nylon (m-xylylene adipamide),nylon with barrier properties (amorphous nylon), polyacrylonitrile,liquid-crystal polyester, all-aromatic nylon (aramid), polyvinyl acetate(PVA) or its hydrolyzate, and the like can be given. A transparentmultilayer film such as PVDC-coated biaxial stretching polyethyleneterephthalate, PVDC-coated biaxial-stretching polypropylene, andPVDC-coated biaxial stretching polyvinyl alcohol, a vapor depositionfilm, and the like may also be used.

Of these, an ethylene-vinyl alcohol copolymer (EVOH) is particularlypreferable due to its excellent gas barrier properties.

In order to compensate insufficient bending strength, flex resistance,and tensile strength of the layer made only of the hydrogenatednorbornene ring-open polymer, the multilayer laminate of the presentinvention may contain at least one layer of a second synthetic resin inplace of, or in combination with, the layer containing a gas barrierresin as the synthetic resin.

Any resin material commonly used for medical application or foodpackaging may be used as the resin material forming the second syntheticresin layer without particular limitations. As examples, varioussynthetic resins such as acrylic resins such as a polyolefin resin,polyamide resin, polyester resin, polymethyl methacrylate,polycarbonate, ionomer resin, polystyrene, ABS resin, thermoplasticelastomer, ethylene-carboxylate copolymer, ethylene-vinyl acetatecopolymer, polysulfone, polyvinyl chloride, and fluororesin can begiven. Among these resins, at least one resin selected from the groupconsisting of a polyolefin resin, a polyamide resin, and a polyesterresin is preferable.

As examples of the polyolefin resin, polyethylene resins such as alinear or branched ethylene-α-olefin copolymer, high densitypolyethylene, low density polyethylene, linear low density polyethylene,and ultra-high molecular weight polyethylene; polypropylene resins suchas homopolypropylene, ethylene-propylene random copolymer,ethylene-propylene block copolymer, ethylene-propylene-1-butenecopolymer; polyolefin resins shown by the group consisting ofethylene-propylene copolymer, polymethylpentene, polybutene,polymethylbutene, polymethylhexene and the like; amorphous polyolefinresins such as alicyclic structure-containing polymers described inJP-A-2001-143323; and the like can be given.

As the polyamide resin, nylon 6, nylon 66, nylon 610, nylon 6T, and thelike can be given.

As examples of polyester resin, polyethylene terephthalate,polybuthylene terephthalate, and polyethylene naphthalate can be given.

These synthetic resin layers are used as a monolayer of a resin or amultilayer laminate of two or more layers. The type of synthetic resinand the layer constitution can be appropriately selected according tothe purpose of use.

As the second synthetic resin layer, a layer containing a polyolefinresin is preferably used, a layer containing polyethylene orpolypropylene is more preferable due to excellent low elusionproperties, chemical resistance, and oil resistance, and a layercontaining polypropylene is particularly preferable due to excellentheat resistance and transparency in addition to the above properties.

The multilayer laminate of the present invention may be combined with atransparent vapor deposition film in order to provide gas barrierproperties and weather (light) resistance.

In addition, a metallic foil such as an aluminum foil, an aluminum vapordeposition film, a laminate film of a metallic foil and a syntheticresin film, a layer which has a light blocking effect (shading layer)such as a synthetic resin film with a pigment incorporated therein maybe provided.

The following combinations of layers can be given as specific examplesof the layer constitution of the multilayer laminate of the presentinvention. In the following constitutions, the layer containing thehydrogenated norbornene ring-open polymer is indicated as “NB layer” andthe other resin layers are indicated as “synthetic resin layer”.

(1) NB layer/synthetic resin layer(2) NB layer/synthetic resin layer/NB layer(3) Synthetic resin layer/NB layer/synthetic resin layer(4) NB layer/synthetic resin layer/synthetic resin layer/NB layer(5) NB layer/synthetic resin layer/NB layer/synthetic resin layer(6) NB layer/synthetic resin layer/NB layer/synthetic resin layer/NBlayer(7) Synthetic resin layer/synthetic resin layer/NB layer/synthetic resinlayer/synthetic resin layer(8) Synthetic resin layer/NB layer/synthetic resin layer/NBlayer/synthetic resin layer(9) NB layer/synthetic resin layer/shading layer(10) NB layer/synthetic resin layer/shading layer/synthetic resin layer(11) NB layer/shading layer

The multilayer bodies of the present invention are not limited to theabove combinations. It is possible to employ other desired multilayerconstitutions according to the purpose of use, such as those having alarger number of layers in addition to any one of the above layercombinations.

For example, when the multilayer laminate of the present inventionincludes a layer containing a resin having gas barrier properties, it isnecessary for such a resin layer to not come in contact with water inorder to maintain the gas barrier performance. For this reason, apacking material made from the multilayer laminate having a gas barrierresin layer of the present invention is preferably provided with a layercontaining the hydrogenated norbornene ring-open polymer on the sidebeing exposed to the outside, when it is desired to prevent permeationof moisture and oxygen from the outside. When the content of the packageis an aqueous solution and the like, it is preferable that a layercontaining the hydrogenated norbornene ring-open polymer be provided onthe side being exposed to the content of the package.

In the multilayer laminate of the present invention, an adhesive layerconsisting of an intercalation adhesive may be optionally providedbetween the layers.

There are no particular limitations to the intercalation adhesiveinsofar as the adhesive does not adversely affect the film properties.As examples, an adhesive rubber, an adhesive thermoplastic resin, anadhesive thermoplastic elastomer, thermosetting adhesives such as anepoxy resin, a silicone resin, and an urethane resin, thermoplasticadhesives such as polyvinyl ether, an acrylic resin, and a vinylacetate-ethylene copolymer, a hotmelt polyamide resin adhesive, rubberadhesives such as nitrile rubber, and the like may be given. Amongthese, a urethane adhesive and an adhesive olefin polymer arepreferable.

The synthetic resin layer of the multilayer laminate of the presentinvention may contain an additive which may be used with thehydrogenated norbornene ring-open polymer.

The multilayer laminate of the present invention may be obtained bymolding the hydrogenated ring-open polymer of the present invention or aresin composition containing the hydrogenated ring-open polymer of thepresent invention and additives, and a resin used for the syntheticresin layer or a resin composition containing the resin used for thesynthetic resin layer and additives by a known molding method.

Although not particularly limited, the method of molding the multilayerlaminate of the present invention includes, for example, a coextrusionmolding method such as a coextrusion T-die method, a coextrusioninflation method, and a coextrusion lamination method; film laminationmolding methods such as dry lamination; a coating mold method in which aresin solution is applied to a substrate resin film, a calendar moldingmethod, a heat press molding method, an injection molding method, andthe like.

The molding conditions are suitably selected according to the type ofthe resin used.

There are no particular limitations to the shape of the multilayerlaminate of the present invention. When used as a packing material, themultilayer laminate may usually be in the form of a film or a sheet, butmay be in the form of a tube.

The multilayer laminate of the present invention may usually beunstretched, but may be stretched as required.

The stretching may be carried out by any method such as a roll method, atenter method, and a tube method. The stretching conditions are suitablyselected according to the type of the resin used.

Although there are no specific limitations, the thickness of themultilayer laminate of the present invention obtained by theabove-mentioned method is usually 5 to 1000 μm, preferably 20 to 500 μm,and more preferably 30 to 300 μm. If the thickness is more than theabove maximum thickness, the multilayer laminate does not havepliability; if the thickness is less than the above minimum thickness,the multilayer laminate has insufficient strength and tends to beruptured easily.

Printing may be applied to the multilayer laminate of the presentinvention.

A common printing method such as letterpress printing, hand gravureprinting, and surface printing may be used without particularlimitation. A suitable printing ink may be appropriately selectedaccording to the printing method. For example, a letterpress ink, aflexographic ink, a dry offset ink, a photogravure ink, a photogravureoffset ink, an offset ink, and a screen ink may be given.

In order to improve adhesion of the ink, it is preferable to apply asurface treatment to the printing layer before applying a printing ink.As the method of surface treatment, a corona discharge treatment, aplasma discharge treatment, a flame treatment, an emboss processingtreatment, a sand mat processing treatment, a satin processingtreatment, and the like can be given.

The multilayer laminate of the present invention is excellent also inimpact resistance. The impact resistance may be confirmed by layeringtwo sheets of the multilayer laminate with a thickness of 50 μm,preparing a 20 cm×20 cm bag by sealing the sides with heat, puttingbrine in the bag, and dropping the bag from a height of 3 m. Thepresence or absence of cracks immediately after dropping is determinedwith the naked eye. Excellent impact resistance can be confirmed ifthere are almost no cracks observed.

The multilayer laminate of the present invention has excellent steambarrier properties. The moisture permeability of the multilayer laminatewith a thickness of 50 μm of the present invention is usually 3 g/(m²·24h) or less, preferably 2.5 g/(m²·24 h) or less.

The steam barrier properties can be measured according to MS K7129(method A), for example, using a moisture permeability tester (L80-5000type, manufactured by LYSSY) under the conditions of a temperature of50° C. and humidity of 90% RH.

The multilayer laminate having at least one layer containing a gasbarrier resin has excellent gas barrier properties. The oxygenpermeability of the multilayer laminate having at least one layercontaining a gas barrier resin with a thickness of 50 of the presentinvention is usually 0.5 cm³·m⁻²·day⁻¹·atm⁻¹ or less, and preferably0.35 cm³·m⁻²·day⁻¹·atm⁻¹ or less.

The multilayer laminate having at least one layer containing a gasbarrier resin shows almost no decrease in the oxygen permeability afterhaving been left under high temperature and high humidity conditions(e.g. after having been left in boiling water for 30 minutes).

The gas barrier properties of the multilayer laminate can be evaluatedby dipping a bag made of the multilayer laminate of the presentinvention in boiling water for 30 minutes and measuring the gas barrierproperties before and after boiling according to JIS K7126 (method B)under the conditions of a temperature of 23° C. and humidity of 0% RHusing an oxygen permeability tester (OPT-5000 type, manufactured byLYSSY), for example.

The multilayer laminate of the present invention is excellent in oilresistance. The oil resistance can be evaluated by cutting a 5 cm squarefrom the film to obtain a sample, dipping the sample in salad oil(manufactured by Nisshin Oillio Group, Ltd.) for 30 seconds, and placingthe sample in an oven heated at 40° C., and measuring the period of timeelapsed before the outward appearance of the sample changes. The oilresistance of the multilayer laminate of the present invention isindicated by the number of days before the film is whitened, which isusually four days, preferably five days, and more preferably six days.

The fields in which the multilayer laminate of the present invention isparticularly useful include, in addition to the fields of foods, medicalsupplies, displays, energy, and other industrial fields, wrappingmaterials for toys, household goods, and the like. A packing materialwith a desired shape and size may be prepared by secondary fabricationof the multilayer laminate of the present invention as mentioned later.

Due to possession of excellent steam barrier properties and impactresistance, the multilayer laminate of the present invention is suitablyused for applications requiring hot water sterilization, retorting, hotfilling, steam sterilization, and the like. When at least one layercontains a gas barrier resin, the multilayer laminate of the presentinvention exhibits only a small change in the gas barrier propertiesunder high temperature and high humidity conditions. For example,medical-related containers or films for packing bags such as an infusionsolution bag, PTP (press-through package), and a syringe; films for afood container or a packing bag and a blister pack such as a retort packrequiring heat sterilization, a jelly or pudding container, a containerfor processed foods such as ham, sausage, and frozen food, containersfor dried food, specified health food, rice, confectionery, and meat, aswell as lids for these containers, and hot-fill containers; a film and ablister pack for packaging containers or packing bag for precisioncomponents such as electric and electronic parts, semiconductor parts,and printed circuit boards; a heat-shrinkable film and blister pack ofpacking material for storing and transporting foods, medicines,instruments, miscellaneous goods such as stationery supplies andnotebooks; a film and a blister pack for tamper-resistant seal packingmaterials such as a cap and a plug; a film for heat-shrinkable labelmaterial for containers, solar energy power generation systemcomponents, fuel cell components, and alcohol-containing fuel systemcomponents, as well as films and blisters for these components; and thelike can be given.

6) Packing Material

The packing material of the present invention is obtained by secondaryfabrication of the multilayer laminate of the present invention.

There are no particular limitations to the method of secondaryfabrication. Press molding, vacuum molding, air-pressure forming,heat-sealing, and melt bonding can be given as examples.

As the manner of heat-sealing, the innermost layer of the multilayerlaminate is folded or two multilayer bodies are layered and theperiphery of the circumference is heat-sealed by side sealing, two-waysealing, three-way sealing, four-way sealing, envelope sealing, pillowsealing, diaphragm sealing, flat bottom sealing, cornered bottomsealing, or the like.

Various generally known heat-sealing methods may be employed withoutparticular limitations. A bar seal method, a rotation roll seal method,a belt seal method, an impulse sealing method, a high frequency sealmethod, and an ultrasonic seal method can be given as examples. Thepacking material may be provided with a one-piece-type or two-piece-typeinjection port, a zipper for opening and closing, and the like.

As a blister molding method for fabricating a pocket, an appropriatemethod such as heat-press forming, drum vacuum forming, plug dieforming, pin molding, preheater pressure forming, preheater plug-assistpressure forming, and the like may be used. A pocket with a shape suchas a cylinder, a dome, an ellipse dome and a size conforming to theobject to be contained may be prepared by the blister molding.

The packing material of the present invention has excellent steambarrier properties, mechanical properties such as impact resistance, andoil resistance, and when possessing at least one layer containing a gasbarrier resin, has excellent gas barrier properties in a hightemperature and high humidity environment. Therefore, the packingmaterial is suitable for a medical supply packing container, a foodpacking container, and the like.

7) Medical Supply Packing Material

The medical supply packing material of the present invention has atleast one resin layer of a layer of a hydrogenated norbornene ring-openpolymer obtained by hydrogenating 80% or more of carbon-carbon doublebonds of a ring-open polymer which is obtained by ring-openingpolymerization of 2-norbornene and a substituent-containing norbornenemonomer, the proportion of a repeating unit (A) derived from the2-norbornene with respect to all repeating units being 90 to 100 wt %and the proportion of a repeating unit (B) derived from thesubstituent-containing norbornene monomer with respect to all repeatingunits being 0 to 10 wt %, and the hydrogenated norbornene ring-openpolymer having a melting point of 110 to 145° C.

Specifically, the hydrogenated norbornene ring-open polymer used as themedical supply packing material of the present invention is the same asthe hydrogenated norbornene ring-open polymer of the present inventiondescribed above, except that weight average molecular weight (Mw)determined by gel permeation chromatography (GPC) or the molecularweight distribution (Mw/Mn) of hydrogenated norbornene ring-open polymermay not be particularly limited, when such a polymer is obtained byhydrogenating 80% or more of main-chain carbon-carbon double bonds of aring-open polymer which is obtained by ring-opening polymerization of2-norbornene (hydrogenated 2-norbornene ring-open polymer). The polymersmentioned above as preferable examples of the hydrogenated norbornenering-open polymer of the present invention are preferable hydrogenatednorbornene ring-open polymers used as the medical supply packingmaterial of the present invention.

The monomer mixture used for producing the hydrogenated norbornenering-open polymer used for the medical supply packing material of thepresent invention comprises usually 90 to 100 wt %, preferably 95 to 99wt %, and more preferably 97 to 99 wt % of 2-norbornene and usually 0 to10 wt %, preferably 1 to 5 wt %, and more preferably 1 to 3 wt % of thesubstituent-containing norbornene monomers.

The proportion of the repeating unit (A) derived from 2-norbornene withrespect to all repeating units of the hydrogenated norbornene ring-openpolymer used for the medical supply packing material of the presentinvention is 90 to 100 wt %, preferably 95 to 99 wt %, and morepreferably 97 to 99 wt %, and the proportion of the repeating unit (B)derived from the substituent-containing norbornene monomer with respectto all repeating units of the hydrogenated norbornene ring-open polymeris 0 to 10 wt %, preferably 1 to 5 wt %, and more preferably 1 to 3 wt%.

Various additives may be added to the hydrogenated norbornene ring-openpolymer used for the medical supply packing material of the presentinvention according to the purpose of application. Examples of theadditives include antioxidants, rubber-like polymers and other resins,UV absorbers, weather-resistant stabilizers, antistatic agents, slippingagents, anticlouding agents, dyes, pigments, coloring agents, naturaloils, synthetic oils, plasticizers, organic or inorganic fillers,antibacterial agents, deodorants, and the like. As specific examples ofthe additives used for the medical supply packing material of thepresent invention, the same additives as those used for the multilayerlaminate of the present invention may be given. As specific examples ofthe additives preferably used for the medical supply packing material ofthe present invention, the same additives as those preferably used forthe multilayer laminate of the present invention may be given.

The medical supply packing material of the present invention may be madeof only a resin layer containing the hydrogenated ring-open polymer ofthe present invention or made of a multilayer laminate which contains,in addition to at least one resin layer containing the hydrogenatednorbornene ring-open polymer of the present invention, a synthetic resinlayer which contains at least one other layer.

The medical supply packing material of the multilayer laminate ispreferable due to increased oil resistance, pliability, impactresistance, heat resistance, and the like.

The content of the hydrogenated ring-open polymer in the resin layerwhich contains the hydrogenated ring-open polymer in the medical supplypacking material of the present invention is usually 50 to 100 wt %,preferably 70 to 100 wt %, and more preferably 90 to 100 wt %. Thecontent of the hydrogenated ring-open polymer in this range ispreferable because the characteristics possessed by the hydrogenatedring-open polymer such as steam barrier properties are not impaired.

Although there are no specific limitations, the thickness of the layercontaining the hydrogenated ring-open polymer is usually 1 to 500 μm,preferably 10 to 150 μm, and more preferably 20 to 100 μm. Thisthickness range is preferable because the characteristics possessed bythe hydrogenated ring-open polymer such as steam barrier properties arenot impaired.

Any resins that are used for medical applications may be used as theother resins without a particular limitation. Examples include varioussynthetic resins such as a polyolefin resin, polyethylene terephthalate,polybuthylene terephthalate, polymethylmethacrylate, polycarbonate,ionomer resin, polystyrene, ABS resin, thermoplastic elastomer, nylon,ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer(EVOH), nylon, polysulfone, and the like.

Among these resins, the polyolefin resin is particularly preferablebecause of its effect of improving mechanical properties, oilresistance, and the like of the medical supply packing material.

As examples of the polyolefin resin, polyolefin crystalline resins shownby the group consisting of polyethylene resins such as a linear orbranched high density polyethylene, low density polyethylene, andultra-high molecular weight polyethylene; polypropylene resins such aslinear or branched high density polypropyrene and low densitypolypropyrene; ethylene-propylene copolymer, polymethylpentene,polybutene, polymethylbutene, and polymethylhexene; and the like can begiven.

Among these, the polyethylene-containing synthetic resin layer ispreferably used for fabricating multilayer laminate. The multilayerlaminate obtained by using such a synthetic resin layer exhibitsexcellent low elusion properties, oil resistance, and chemicalresistance. Furthermore, low density polyethylene, which has a densityof 0.88 to 0.94 g/cm³ measured according to JIS K6922, has superiortransparency in addition to these excellent properties.

In addition, a gas barrier resin such as an ethylene-vinyl alcoholcopolymer, nylon, or the like is preferable as a layer to be laminatedto promote the gas barrier properties of the resulting multilayerlaminate.

In the medical supply packing material of the present invention, inaddition to the resin layer containing the hydrogenated ring-openpolymer and the synthetic resin layer containing the other resins, ametallic foil such as an aluminum foil, an aluminum vapor depositionfilm, a laminate film of a metallic foil and a synthetic resin film, alayer which has a light blocking effect (shading layer) such as asynthetic resin film with a pigment incorporated therein may beprovided.

There are no particular limitations to the constitution of themultilayer laminate used for the medical supply packing material of thepresent invention inasmuch as such a multilayer laminate contains atleast the resin layer containing the hydrogenated ring-open polymer andthe synthetic resin layer containing the other resins. As specificexamples, the following combinations of layers can be given. In thefollowing constitutions, the resin layer containing the hydrogenatedring-open polymer is indicated as “NB layer” and the synthetic resinlayers containing the other resin are indicated as “synthetic resinlayer”.

(1) NB layer/synthetic resin layer(2) NB layer/synthetic resin layer/NB layer(3) Synthetic resin layer/NB layer/synthetic resin layer(4) NB layer/synthetic resin layer/synthetic resin layer/NB layer(5) NB layer/synthetic resin layer/NB layer/synthetic resin layer(6) NB layer/synthetic resin layer/NB layer/synthetic resin layer/NBlayer(7) Synthetic resin layer/synthetic resin layer/NB layer/synthetic resinlayer/synthetic resin layer(8) Synthetic resin layer/NB layer/synthetic resin layer/NBlayer/synthetic resin layer(9) NB layer/synthetic resin layer/shading layer(10) NB layer/synthetic resin layer/shading layer/synthetic resin layer(11) NB layer/shading layer

It is possible to employ other desired multilayer constitutionsaccording to the purpose of use, such as those having a larger number oflayers in addition to any one of the above layer combinations.

In the medical supply packing material of the present invention, anadhesive layer may be optionally provided between the layers.

As the adhesive, the same adhesives that are given as the adhesive to beused in the multilayer laminate can be given.

In the synthetic resin layer of the medical supply packing material ofthe present invention, the synthetic resin layer which contains theother resins may contain additives which may be used with thehydrogenated norbornene ring-open polymer.

When the medical supply packing material of the present invention is amonolayer material, such a monolayer material may be obtained by moldingthe hydrogenated ring-open polymer of the present invention or a resincomposition containing the hydrogenated ring-open polymer and additives(hereinafter may be referred to from time to time as “resin composition(1)”) by a known molding method.

As an example of the method for preparing the resin composition (1), amethod of melt-kneading the hydrogenated ring-open polymer and theadditives using a twin-screw kneader, for example, at 200 to 400° C.,and producing pellets, granules, or powder from the kneaded product canbe given.

There are no particular limitations to the method of molding thehydrogenated ring-open polymer or the resin composition (1). Generallyknown methods, for example, the molding method such as a T-die method,an inflation method, or a lamination method; the film lamination moldmethod such as dry lamination; heat-press molding method; injectionmolding method; and the like may be appropriately used. The moldingconditions are suitably selected according to the type of the resinused.

When the medical supply packing material of the present invention is amultilayer material, such a multilayer material may be obtained bymolding the hydrogenated ring-open polymer or the resin composition (1)and a resin composition containing the other resin and other additives(hereinafter may be referred to from time to time as “resin composition(2)”) by a known molding method.

The resin composition (2) may be prepared in the same manner as theresin composition (1).

In the present invention, the molded article may be annealed in order toincrease crystallinity.

In order to increase the mechanical properties and steam barrierproperties, the medical supply packing material may be stretched toincrease the crystallinity. This is an operation of applying plasticdeformation to a sheet or film by stretching the length of the moldedfilm or sheet 1.1 to 10 times. The plastic deformation has an effect oforienting amorphous chains, not to mention of crystalline chains, byinternal friction caused by stretching.

The medical supply packing material of the present invention may beusually a film or a sheet, but may be a tube. If processed by aninflation method, the product has a form of a tube (a cylinder). A bagcan be prepared by a simple process of cutting the tube and sealing oneopen side. When the inflation method is used, it is preferable to have adie lip clearance of 2.5 mm or more in order to prevent melt flowfracture due to the shearing stress when the resin is extruded at a highspeed (8 m/min or more).

In this instance, the molding temperature in terms of the dietemperature is preferably 180 to 210° C. If the die temperature is 210°C. or higher, burning (discoloration) and fish eyes tend to occur easilyand film formation (molding) becomes difficult due to a decrease of meltviscosity. The screw compression ratio is preferably not more than 3.0.If the screw compression ratio is more than 3.0, self-heating mayincrease and molding will become difficult.

Although there are no specific limitations, the thickness of the medicalsupply packing material obtained in the manner as described above isusually 100 to 500 μm, preferably 150 to 350 μm, and still morepreferably 200 to 300 μm. If the thickness of the packing material ismore than the above maximum thickness, the film does not havepliability; if the thickness is less than the above minimum thickness,the medical supply packing material has insufficient strength and tendsto rupture easily.

The medical supply packing material of the present invention may beobtained by molding the hydrogenated ring-open polymer or the resincomposition (1) or the hydrogenated ring-open polymer or the resincomposition (1) and the other resin or the resin composition (2) into afilm or a sheet and subjecting the film or the sheet to secondaryprocessing.

Although not particularly limited, press molding, vacuum molding,pressure forming, heat-sealing, and melt bonding can be given asexamples of the secondary processing. Of these, heat-sealing ispreferable.

As the manner of heat-sealing, the innermost layer of the multilayerfilms or multilayer sheets is folded or two multilayer sheets or filmsare layered and the periphery of the circumference is heat-sealed byside sealing, two-way sealing, three-way sealing, four-way sealing,envelope sealing, pillow sealing, diaphragm sealing, flat bottomsealing, cornered bottom sealing, or the like.

Various generally known heat-sealing methods may be employed withoutparticular limitation. A bar seal method, a rotation roll seal method, abelt seal method, an impulse sealing method, a high frequency sealmethod, and an ultrasonic seal method can be given as examples. Thepackaging material may be provided with a one-piece-type ortwo-piece-type injection port, a zipper for opening and closing, and thelike.

The medical supply packing material of the present invention obtained inthe above-described manner only has small unevenness in the filmthickness. If unevenness of the film thickness is large and thethickness varies in different areas of the film, the rolled-up filmcontains hard swollen portions (lumps) which cause a problem duringprinting or heat-sealing.

An uneven film thickness of the medical supply packing material of thepresent invention can be evaluated by, for example, applying five markson the film at 4 cm intervals in the direction (TD direction) verticalto the flow direction of the film, applying 20 marks at 20 cm intervalsin the flow direction (MD direction) of the film starting from the firstfive marks, thereby applying 100 marks in total, and measuring the filmthickness at the 100-mark points. The smaller the value of the standarddeviation calculated from the thickness measurement result, the smallerthe thickness unevenness. In the medical supply packing material of thepresent invention, the standard deviation of a film with a thickness of250 μm is not more than 10 μm.

The medical supply packing material of the present invention obtained inthis manner has excellent steam barrier properties. The medical supplypacking material of the present invention with a thickness of 250 μm hasmoisture permeability measured based on JIS K7129 (Method A) at atemperature of 50° C. at 90% RH of usually 2 g/(m²·24 h) or less,preferably 1.5 g/(m²·24 h) or less, and more preferably 1 g/(m²·24 h) orless. If the moisture permeability is within this range, mixing ofmoisture into the medicine packed in the medical supply packing materialis suppressed and quality deterioration of the drug can be prevented.

The medical supply packing material of the present invention has anexcellent modulus of elasticity. It is desirable that modulus ofelasticity of a sample of the medical supply packing material of thepresent invention having an IB shape and a thickness of 250 μm measuredaccording to ISO 527 at a tensile velocity of 200 mm/min using Autograph(AGS-5kNH, manufactured by Shimadzu Corp.) is not more than 500 MPa. Ifthe modulus of elasticity is not more than 500 MPa, the medical supplypacking material has excellent pliability and can transfer a medicalfluid at a uniform flow rate when used as an infusion solution bag. Ifthe modulus of elasticity is more than 500 MPa, on the other hand, theinfusion solution bag is hard and it is difficult to transfer a medicalfluid at a uniform flow rate.

The medical supply packing material of the present invention also hasexcellent oil resistance. When the oil resistance evaluation value (hazeof untreated sample/haze after applying salad oil) is 0.8 or more, themedical supply packing material is resistant to oil and has itsappearance or performance impaired only with difficulty when oil isattached to the surface.

The medical supply packing material of the present invention hasexcellent mechanical properties. Distortion of the medical supplypacking material of the present invention at the time of a surface crackmeasured using a sample having an IB shape and a thickness of 250 μmaccording to ISO 527 at a tensile velocity of 200 mm/min using Autograph(AGS-5kNH, manufactured by Shimadzu Corp.) is usually 20% or more,preferably 25% or more, and more preferably 30% or more. When thedistortion is within this range, cracks and ruptures occur only withdifficulty in the medical supply packing material.

As specific examples of the medical supply packing material, amedical-related container such as an infusion solution bag and a PTP(press through package); a film or a sheet for packing a syringe; andthe like can be given. An infusion solution bag is the particularlypreferable application.

8) Blister Molding Sheet

The blister molding sheet of the present invention has at least onelayer of a resin which is obtained by hydrogenating 80% or more ofcarbon-carbon double bonds of a ring-open polymer obtained byring-opening polymerization of 2-norbornene or a monomer mixture of2-norbornene and a substituent-containing norbornene monomer, theproportion of a repeating unit (A) derived from the 2-norbornene withrespect to all repeating units being 90 to 100 wt % and the proportionof a repeating unit (B) derived from the substituent-containingnorbornene monomer in all repeating unit being 0 to 10 wt %, and thehydrogenated norbornene ring-open polymer having a melting point of 110to 145° C.

Specifically, the hydrogenated norbornene ring-open polymer used as theblister molding sheet of the present invention is the same as thehydrogenated norbornene ring-open polymer of the present inventiondescribed above, except that the weight average molecular weight (Mw)determined by gel permeation chromatography (GPC) or the molecularweight distribution (Mw/Mn) of the hydrogenated norbornene ring-openpolymer may not be particularly limited if such a polymer is obtained byhydrogenating 80% or more of main-chain carbon-carbon double bonds of aring-open polymer which is obtained by ring-opening polymerization of2-norbornene (hydrogenated 2-norbornene ring-open polymer). The polymersmentioned above as preferable examples of the hydrogenated norbornenering-open polymer of the present invention are preferable hydrogenatednorbornene ring-open polymers used as the blister molding sheet of thepresent invention.

The monomer mixture used for producing the hydrogenated norbornenering-open polymer used for the blister molding sheet of the presentinvention comprises usually 90 to 100 wt %, preferably 95 to 99 wt %,and more preferably 97 to 99 wt % of 2-norbornene and usually 0 to 10 wt%, preferably 1 to 5 wt %, and more preferably 1 to 3 wt % ofsubstituent-containing norbornene monomers.

The proportion of the repeating unit (A) derived from 2-norbornene withrespect to all repeating units of the hydrogenated norbornene ring-openpolymer used for the blister molding sheet of the present invention isusually 90 to 100 wt %, preferably 95 to 99 wt %, and more preferably 97to 99 wt %, and the proportion of the repeating unit (B) derived fromthe substituent-containing norbornene monomer with respect to allrepeating units of the hydrogenated norbornene ring-open polymer is 0 to10 wt %, preferably 1 to 5 wt %, and more preferably 1 to 3 wt %.

Various additives may be added to the hydrogenated norbornene ring-openpolymer used for the blister molding sheet of the present inventionaccording to the purpose of application. Examples of the additivesinclude antioxidants, rubber-like polymers and other resins, UVabsorbers, weather-resistant stabilizers, antistatic agents, slippingagents, anticlouding agents, dyes, pigments, coloring agents, naturaloils, synthetic oils, plasticizers, organic or inorganic fillers,antibacterial agents, deodorants, and the like. As specific examples ofthe additives used for the blister molding sheet of the presentinvention, the same additives as those used for the multilayer laminateof the present invention may be given. As specific examples of theadditives preferably used for the medical supply packing material of thepresent invention, the same additives as those preferably used for themultilayer laminate of the present invention may be given.

The blister molding sheet of the present invention has at least oneresin layer containing the hydrogenated ring-open polymer of the presentinvention. The blister molding sheet of the present invention mayconsist only of a layer containing the hydrogenated ring-open polymer ormay be a multilayer laminate further comprising at least one syntheticresin layer containing another resin.

The content of the hydrogenated ring-open polymer in the resin layerwhich contains the hydrogenated ring-open polymer in the blister moldingsheet of the present invention is usually 50 to 100 wt %, preferably 70to 100 wt %, and more preferably 90 to 100 wt %. The content in thisrange is preferable because the characteristics possessed by thehydrogenated ring-open polymer such as steam barrier properties are notimpaired.

Although there are no specific limitations, the thickness of the layercontaining the hydrogenated norbornene ring-open polymer is usually 5 to1000 μm, preferably 5 to 500 μm, more preferably 10 to 300 μm, and stillmore preferably 20 to 200 μm. The thickness in the above range ispreferable because the characteristics possessed by the hydrogenatedring-open polymer such as steam barrier properties are not impaired.

Any resin material commonly used for packing foods, medical supplies,industrial parts, and the like may be used as the other resins. Asexamples, various synthetic resins such as a polyolefin resin,polyethylene terephthalate, polybuthylene terephthalate, polymethylmethacrylate, polycarbonate, ionomer resin, polystyrene, ABS resin,thermoplastic elastomer, nylon, ethylene-carboxylate copolymer,ethylene-carboxylic acid copolymer, ethylene-vinyl acetate copolymer,ethylene-vinyl alcohol copolymer (EVOH), nylon, polysulfone, polyvinylchloride, polyvinylidene chloride, and fluororesin can be given.

These synthetic resin layers are used as a monolayer of a resin or amultilayer laminate of two or more layers. The type of the syntheticresin and the layer constitution can be appropriately selected accordingto the purpose of use.

The blister molding sheet of a multilayer laminate is preferable due toincreased mechanical properties, oil resistance, blister moldability,and the like. Among the above synthetic resin layers, a synthetic resinlayer containing a polyolefin resin layer or a layer containing a gasbarrier resin such as an ethylene-vinyl alcohol copolymer, nylon, or apolyvinylidene chloride as another layer is preferable.

As examples of the polyolefin resin, polyolefin-based crystalline resinsshown by the group consisting of a linear or branched ethylene-α-olefincopolymer, polyethylene resins such as high density polyethylene, lowdensity polyethylene, linear low density polyethylene, and ultra-highmolecular weight polyethylene; polypropylene resins such ashomopolypropylene, an ethylene-propylene random copolymer, anethylene-propylene block copolymer, and an ethylene-propylene-1-butenecopolymer; an ethylene propylene copolymer, polymethylpentene,polybutene, polymethylbutene, polymethylhexene and the like; alicyclicstructure-containing polymer resins such as a norbornene polymer, amonocycle cycloolefin polymer, a cyclic conjugated diene polymer, avinyl alicyclic hydrocarbon polymer, and hydrogenated products of thesepolymers described in JP-A-2001-143323; and the like can be given.

Among these, the synthetic resin layer containing polyethylene orpolypropylene is more preferable due to excellent low elusionproperties, chemical resistance, and oil resistance, and a layercontaining polypropylene is particularly preferable due to excellentheat resistance and transparency in addition to the above properties.

In addition, a layer containing a gas barrier resin as the syntheticresin layer containing other resins is preferable to improve gas barrierproperties.

The blister molding sheet of the present invention may be combined witha transparent vapor deposition film in order to provide gas barrierproperties and weather (light) resistance.

In addition, the blister molding sheet of the present invention may beprovided with a metallic foil such as an aluminum foil, an aluminumvapor deposition film, a laminate of a metallic foil and a syntheticresin film, a layer which has a light blocking effect (shading layer)such as a synthetic resin film with a pigment incorporated therein.

The synthetic resin layer and the shading layer of the blister moldingsheet of the present invention may be a laminate of two or more layers.

It is possible to employ a desired multilayer constitution according tothe purpose of use of the blister molding sheet. There are no particularlimitations to the constitution of the multilayer laminate used for theblister molding sheet of the present invention inasmuch as such amultilayer laminate contains a layer of the hydrogenated ring-openpolymer of the present invention and a layer of the other material. Inthe following constitutions, the resin layer containing the hydrogenatedring-open polymer is indicated as “NB layer” and the synthetic resinlayers containing the other resin are indicated as “synthetic resinlayer”.

(1)NB layer/synthetic resin layer(2) NB layer/synthetic resin layer/NB layer(3) Synthetic resin layer/NB layer/synthetic resin layer(4) NB layer/synthetic resin layer/synthetic resin layer/NB layer(5) NB layer/synthetic resin layer/NB layer/synthetic resin layer(6) NB layer/synthetic resin layer/NB layer/synthetic resin layer/NBlayer(7) Synthetic resin layer/synthetic resin layer/NB layer/synthetic resinlayer/synthetic resin layer(8) Synthetic resin layer/NB layer/synthetic resin layer/NBlayer/synthetic resin layer(9) NB layer/synthetic resin layer/shading layer(10) NB layer/synthetic resin layer/shading layer/synthetic resin layer(11) NB layer/shading layer

In the blister molding sheet of the present invention, an adhesive layermay be optionally provided between the layers.

As specific examples of the adhesive which forms the adhesive layer, anadhesive rubber, an adhesive thermoplastic resin, an adhesivethermoplastic elastomer, thermosetting adhesives such as an epoxy resin,a silicone resin, and a urethane resin, thermoplastic adhesives such aspolyvinyl ether, an acrylic resin, and a vinyl acetate-ethylenecopolymer, a hotmelt polyamide resin adhesive, rubber adhesives such asnitrile rubber, and the like may be given. Although there are nospecific limitations to the extent that the properties of the film arenot affected, a urethane adhesive and an adhesive olefin polymer arepreferable among these adhesives.

The synthetic resin layer of the blister molding sheet of the presentinvention may contain an additive which may be used with thehydrogenated norbornene ring-open polymer.

The method for molding the blister molding sheet of the presentinvention includes, for example, molding methods such as a T-die method,an inflation method, and a coextrusion T-die method, a coextrusioninflation method, a coextrusion lamination method; film laminationmolding methods such as dry lamination; a coating mold method in which aresin solution is applied to a substrate resin film, a calendar moldingmethod, a heat press molding method, an injection molding method, andthe like.

The molding conditions are suitably selected according to the type ofthe resin used.

The blister molding sheet of the present invention may be usuallyunstretched, but may be stretched as required. Stretching can increasethe degree of crystallization, mechanical properties, and steam barrierproperties.

The stretching may be carried out by any method such as a roll method, atenter method, and a tube method. Although the stretching conditions aresuitably selected according to the type of the sheet used, the sheet isusually stretched about 1.1 to 10 times.

The blister molding sheet of the present invention obtained by theabove-mentioned method has a thickness of usually 5 to 1000 μm,preferably 10 to 500 μm, more preferably 30 to 400 μm, and still morepreferably 40 to 300 μm. If the thickness of the blister molding sheetis more than the above maximum thickness, the sheet does not havepliability; if the thickness is less than the above minimum thickness,the blister molding sheet has insufficient strength and tends torupture.

As desired, printing may be applied to the blister molding sheet of thepresent invention.

A common printing method such as letterpress printing, hand gravureprinting, and surface printing may be used without a particularlimitation. A suitable printing ink may be appropriately selectedaccording to the printing method. For example, a letterpress ink, aflexographic ink, a dry offset ink, a photogravure ink, a photogravureoffset ink, an offset ink, and a screen ink may be given.

In order to improve adhesion of the ink, it is preferable to apply asurface treatment to the printing layer before applying a printing ink.As the method of surface treatment, a corona discharge treatment, aplasma discharge treatment, a flame treatment, an emboss processingtreatment, a sand mat processing treatment, a satin processingtreatment, and the like can be given.

The fields in which the blister molding sheet of the present inventionis particularly useful include, in addition to the fields of foodindustries, medical supplies, displays, energy, and other industrialfields, toys, household goods, and the like. Since the blister moldingsheet does not produce a thickness variation during blister molding, hasexcellent mechanical strength, and particularly exhibits only a minimalchange in the steam barrier properties according to the change inenvironment, the blister molding sheet is suitable for packing goods tobe preserved for a long period of time under natural environmentalconditions. For example, the blister molding sheet is suitable for useas a container or a blister pack for medical supplies such as a pressthrough package (PTP), a syringe, and the like; foods; precisioncomponents such as electric and electronic parts, semiconductor parts,printed circuit boards; solar energy power generation system components;fuel cell components; alcohol-containing fuel system components; and thelike.

9) Blister Molded Article

The blister molded article of the present invention is obtained byforming the blister molding sheet of the present invention.

Specifically, a blister molded article may be obtained by forming theblister molding sheet by a commonly known method to batch-wisely orcontinuously prepare plastic sheets having one or more concave portions(pockets) to store goods therein (blister molding) and, as required,folding two sides or three sides among the left, right, top and bottomsides with heating (sheet processing) to form cuff parts for insertingsubstrates or mat boards so that the concave portions may be blocked.

There are no specific limitations to the blister molding method forforming the pockets. For example, (i) a flat board blow molding methodof softening the blister molding sheet of the present invention withheat, putting the softened sheet between a lower mold which has a holeto which a high pressure air is supplied and an upper mold which has apocket-shaped recess, and feeding air to form pockets, (ii) a drumvacuum molding method of softening the blister molding sheet of thepresent invention with heat and drawing a pocket-shaped recessed portionof a drum having the recessed portion to form pockets, (iii) a plugmolding method of softening a pocket-shaped concavo-convex die andpressure-bonding the blister molding sheet of the present invention, and(iv) a plug assist blow molding method of assisting the operation ofblow molding in the method (i) by elevating and then moving aconvex-shaped plug downward can be given.

The molding conditions are suitably selected according to the type ofthe blister molding sheet used.

Although there are no particular limitations, heat-sealing, meltbonding, and the like can be given as the method of sheet processingafter blister molding.

Various generally known heat-sealing methods may be employed withoutparticular limitation. A bar seal method, a rotation roll seal method, abelt seal method, an impulse sealing method, a high frequency sealmethod, and an ultrasonic seal method can be given as examples.

The blister molded article may be provided with a one-piece-type ortwo-piece-type injection port, a zipper for opening and closing, and thelike.

The blister molded article of the present invention obtained in thismanner has excellent steam barrier properties. The blister molded sheetof the present invention with a thickness of 250 μm has moisturepermeability at 50° C. and 90% RH usually of 0.5 g/(m²·24 h) or less,preferably 0.4 g/(m²·24 h) or less, and more preferably 0.3 g/(m²·24 h)or less. If the blister molded sheet has poor steam barrier properties,moisture may mingle with a medication in the PTP and may cause thequality of the medication to deteriorate when the blister molded sheetis used as a PTP for packing the medication.

The blister molded article of the present invention has excellent oilresistance. The oil resistance of the blister molded article can beevaluated by applying salad oil (manufactured by Nisshin Oillio Group,Ltd.) to the convex side (projection side) of the blister molded articleand placing the blister molded article in an oven heated at 40° C., andmeasuring the period of time elapsed before the outward appearancechanges. That period of time is usually four days, preferably five days,more preferably six days, and particularly preferably eight days.

The blister molding sheet of the present invention has excellent blistermoldability. The blister moldability (recess of the pocket portion) ofthe blister molding sheet of the present invention may be evaluated byarbitrarily selecting ten sheets of PTP (number of pockets: fivelengthwise, two in the lateral direction, ten pockets in total),visually inspecting cylindrical areas of 100 PTPs to count the number ofthe cylindrical areas of which the bottom is inwardly dented or of whichthe swelling is defective. The number of such defective cylindricalareas is usually not more than 10, preferably not more than 5, morepreferably 1 or 0, and particularly preferably 0.

If there is an unevenness in the pocket of a blister molded articlewhich is processed as a PTP, the bottom of the cylindrical upper part ofthe pocket may inwardly dent or the cylindrical part may inadequatelyexpand. Blister moldability can be evaluated by evaluating such a dentand inadequate expansion.

As specific examples of the blister molded article, containers andblister packs for medical supplies such as a press through package(PTP), a syringe, and the like; foods; precision components such aselectric and electronic parts, semiconductor parts, printed circuitboards; solar energy power generation system components; fuel cellcomponents; alcohol-containing fuel system components; and the like maybe given.

As an example of the method for preparing the resin composition, amethod of melt-kneading the hydrogenated norbornene ring-open polymer ofthe present invention together with an Antioxidant And other optionaladditives using a twin-screw kneader, for example, at 200 to 400° C.,and producing pellets, granules, or powder from the kneaded product canbe given.

10) Blow-Molded Container

The blow-molded container has at least one resin layer of a hydrogenatednorbornene ring-open polymer obtained by hydrogenating 80% or more ofcarbon-carbon double bonds of a ring-open polymer which is obtained byring-opening polymerization of 2-norbornene or a monomer mixture of2-norbornene and a substituent-containing norbornene monomer. Theproportion of a repeating unit (A) derived from the 2-norbornene withrespect to all repeating units is 90 to 100 wt % and the proportion of arepeating unit (B) derived from the substituent-containing norbornenemonomer with respect to all repeating units is 0 to 10 wt %. Thehydrogenated norbornene ring-open polymer has a melting point of 110 to145° C.

Specifically, the hydrogenated norbornene ring-open polymer used as theblow-molded container of the present invention is the same as thehydrogenated norbornene ring-open polymer of the present inventiondescribed above, except that the weight average molecular weight (Mw)determined by gel permeation chromatography (GPC) or the molecularweight distribution (Mw/Mn) of the hydrogenated norbornene ring-openpolymer may not be particularly limited, when such a polymer is obtainedby hydrogenating 80% or more of main-chain carbon-carbon double bonds ofa ring-open polymer which is obtained by ring-opening polymerization of2-norbornene (hydrogenated 2-norbornene ring-open polymer). The polymersmentioned above as preferable examples of the hydrogenated norbornenering-open polymer of the present invention are preferable hydrogenatednorbornene ring-open polymers used as the blow-molded container of thepresent invention.

The monomer mixture used for producing the hydrogenated norbornenering-open polymer used for the blow-molded container of the presentinvention comprises usually 90 to 100 wt %, preferably 95 to 99 wt %,and more preferably 97 to 99 wt % of 2-norbornene and usually 0 to 10 wt%, preferably 1 to 5 wt %, and more preferably 1 to 3 wt % of thesubstituent-containing norbornene monomers.

The proportion of the repeating unit (A) derived from 2-norbornene withrespect to all repeating units of the hydrogenated norbornene ring-openpolymer used for the blow-molded container of the present invention isusually 90 to 100 wt %, preferably 95 to 99 wt %, and more preferably 97to 99 wt %, and the proportion of the repeating unit (B) derived fromthe substituent-containing norbornene monomer with respect to allrepeating units of the hydrogenated norbornene ring-open polymer is 0 to10 wt %, preferably 1 to 5 wt %, and more preferably 1 to 3 wt %.

Various additives may be added to the hydrogenated norbornene ring-openpolymer used for the blow-molded container of the present inventionaccording to the purpose of application. Examples of the additivesinclude antioxidants, rubber-like polymers and other resins, UVabsorbers, weather-resistant stabilizers, antistatic agents, slippingagents, anticlouding agents, dyes, pigments, coloring agents, naturaloils, synthetic oils, plasticizers, organic or inorganic fillers,antibacterial agents, deodorants, and the like. As specific examples ofthe additives used for the blow-molded container of the presentinvention, the same additives as those used for the multilayer laminateof the present invention can be given. As specific examples of theadditives preferably used for the blow-molded container of the presentinvention, the same additives as those preferably used for themultilayer laminate of the present invention can be given.

The blow-molded container of the present invention is a monolayer ormultilayer container obtained by blow molding the hydrogenatednorbornene ring-open polymer alone or together with other thermoplasticresins.

As the method of blow molding, a method commonly used for blow moldingof thermoplastic resins such as direct blow molding, injection blowmolding, stretch blow molding, and multilayer blow molding may be used.Among these methods, monolayer or multilayer stretch blow molding ispreferable. The method of blow molding will now be described mainlytaking the stretch blow molding as an example.

In the stretch blow molding, a preform with a bottom is first preparedby injecting the hydrogenated norbornene ring-open polymer or a mixtureof the hydrogenated norbornene ring-open polymer and the otherthermoplastic resin. Then, after adjusting the temperature, the preformis molded by biaxial stretching blow molding to obtaine a monolayer ormultilayer blow-molded article.

The cylinder temperature during molding the preform is preferably 120 to350° C., more preferably 150 to 300° C., and particularly preferably 160to 250° C. The cylinder temperature in this range ensures appropriatemelt flowability of the resin while suppressing thermal decomposition toobtain a blow-molded container with minimal distortion.

The pressure during perform molding is usually from 0.5 to 100 MPa, andpreferably from 1 to 50 MPa. The pressure is applied usually for aboutseveral seconds to several tens of minutes.

The preform molded by an injection mold is parted from the injectionmold at an injection mold temperature preferably from (Tm−150° C.) to(Tm−10° C.), wherein Tm is a melting point. The injection moldtemperature in this range is preferable from the viewpoint of preformshape stability.

When a heating instrument such as a heating pot is used for controllingthe preform temperature, the temperature of the heating instrument isset preferably from 80 to 400° C., more preferably from 100 to 300° C.,and particularly preferably from 120 to 200° C. If the set temperatureis too low, the heating instrument cannot sufficiently function when thepreform is heated again; if the temperature is too high, the surface ofthe preform and the blow-molded container may be yellowed or produceburnt foreign matter.

Although there are no particular limitations, the distance between theheating instrument and preform is preferably 1 to 50 mm, more preferably2 to 25 mm, and particularly preferably 3 to 10 mm. If the distancebetween the heating instrument and preform is in this range, the riskfor the heating instrument to come in contact with the preform isminimized and the preform can be homogeneously heated.

The blow mold die temperature is appropriately selected according to thetype of the hydrogenated ring-open polymer preferably from a range of(Tm−150° C.) to (Tm−10° C.), and more preferably (Tm−130° C.) to (Tm−10°C.), wherein Tm is the melting point of the hydrogenated ring-openpolymer. If the blow mold die temperature is in this range, the residualstress decreases and the dimension of the container is stabilized duringstoring for a long time. The blow pressure of pressurized air orpressurized nitrogen used per one preform is usually 0.1 to 5 MPa,preferably 0.3 to 3 MPa, and more preferably 0.5 to 1 MPa.

In the case of multilayer blow molding of the hydrogenated norbornenering-open polymer and another thermoplastic resin, these blow moldingconditions are suitably adjusted taking the blow molding conditions ofthe other thermoplastic resin into consideration.

In the process for manufacturing a multilayer preform, molten resins areco-injected into a single preform die cavity through one gate in one dieclamping operation by a sequential molding method or a simultaneousmolding method using a molding machine having a plural injectioncylinders.

In the sequential molding method, injection timing of each resin isadjusted to continuously and alternately inject resins so that themultilayer preform may be produced by disposing the resin injectedearlier in inner/outer layers and disposing the resin injected later inthe middle layer. In the simultaneous molding method, injection timingof each molten resin from the injection cylinder is adjusted so that, atthe initiation, a first resin is injected first and a second resin isinjected later. The two resins are injected simultaneously andcontinuously to produce a multilayer preform with the first resin in theinner/outer layers and the second resin in the middle layer.

The blow molded container of the present invention is preferably astretch blow molded-container. In the stretch blow molding process,after adjusting to a stretchable temperature, the monolayer ormultilayer preform is inserted into a blow molding die cavity, and apressurized fluid such as air is blown into the cavity to carry out blowmolding.

The stretch blow molding may be carried out by either a hot parisonsystem or a cold parison system.

A stretch magnification y in the vertical direction in the stretch blowmolding refers to a ratio of the length below the neck of a blow-moldedcontainer (stretched part) to the length of the preform below the neck(unstretched part), and a stretch magnification x in the horizontaldirection refers to the ratio of the maximum diameter of the containerin the horizontal direction to the maximum diameter of the preform inthe horizontal direction. The maximum diameter refers to the greatestdiameter when the section of the preform and the blow-molded containerare circular and to the greatest equivalent diameter when the section isa polygon or an ellipse form.

The stretch magnification y in the vertical direction is preferably 1.1to 25, more preferably 1.2 to 15, still more preferably 1.5 to 10, andparticularly preferably 1.8 to 8. The stretch magnification x in thehorizontal direction is preferably 1.1 to 25, more preferably 1.2 to 15,still more preferably 1.5 to 10, and particularly preferably 1.7 to 5.When the stretch magnification y in the vertical direction and thestretch magnification x in the horizontal direction are within theseranges, a stretched blow molded article having excellent transparencyand producing cracks only with difficulty in the drop test can beobtained.

The thickness of the blow-molded container is usually 0.1 to 30 mm,preferably 0.3 to 15 mm, and more preferably 0.5 to 10 mm. Theblow-molded container has a size of usually 10 to 2000 mm, andpreferably 50 to 2000 mm in all of the width, depth, and length. Aproduct obtained by sheet blow molding has a flat shape with a width ofusually 10 to 2000 mm, and preferably 50 to 1000 mm and a depth ofusually 0.1 to 100 mm, and preferably 0.5 to 50 mm.

The content of the hydrogenated norbornene ring-open polymer in thelayer which contains the hydrogenated norbornene ring-open polymer inthe blow-molded container of the present invention is usually 50 to 100wt %, preferably 70 to 100 wt %, and more preferably 90 to 100 wt %.This thickness range is preferable because the characteristics possessedby the hydrogenated norbornene ring-open polymer such as steam barrierproperties are not affected.

The thickness of the hydrogenated norbornene ring-open polymer in thelayer which contains the hydrogenated norbornene ring-open polymer inthe blow-molded container of the present invention is usually 0.005 to30 mm, preferably 0.01 to 10 mm, and more preferably 0.05 to 5 mm. Thisthickness range is preferable because the characteristics possessed bythe layer containing the hydrogenated norbornene ring-open polymer suchas steam barrier properties are not affected.

The blow-molded container may have a shape of a cylinder, a squarepillar, a globe, and the like. The cylinder and square pillar arepreferable from the viewpoint of impact strength and the like. Theblow-molded container may also have a skirt-like shape spreading fromthe opening toward the bottom, a shape with a swelling in the centralpart in the height direction, or the like. There are no particularlimitations to the bottom shape of the blow-molded article. Theblow-molded article may have a flat shape or a shape with a depressedportion toward the inside.

The blow-molded container of the present invention may be provided witha painted pattern design, a printed ornament, and the like on thesurface or a part thereof A surface treatment may be applied to theblow-molded container in order to increase adhesiveness of a printinglayer to the blow-molded container. As specific examples of the surfacetreatment, a corona discharge treatment, a plasma treatment, a flametreatment, a resin application, and a hot stamp can be given.

The blow-molded container may be annealed in order to acceleratecrystallization.

Since the hydrogenated norbornene ring-open polymer of the presentinvention is a crystalline polymer having a melting point, if crystalareas are formed in the polymer forming the blow-molded container, thecrystal areas provide the molded container with good mechanicalproperties in combination with amorphous areas, and yet the polymermaintains excellent transparency due to a small degree of crystallinity.

The blow-molded container of the present invention may be a multilayerblow-molded container having a layer of the hydrogenated norbornenering-open polymer and another thermoplastic resin layer. Any resinmaterial commonly used for food and medical application may be used asthe resin forming the layer of the other thermoplastic resin withoutparticular limitations.

As examples of the thermoplastic resin, various synthetic resins, forexample, polyolefin resins such as polyethylene and polypropylene;thermoplastic polyester resins such as polyethylene terephthalate andpolybuthylene terephthalate; gas barrier resins such as polyvinylidenechloride, ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol,and polyamide; polymethyl methacrylate, polycarbonate, ionomer resin,polystyrene, ABS resin, thermoplastic elastomer, ethylene-vinyl acetatecopolymer, and polysulfone can be given.

As examples of the polyolefin resin, polyolefin crystalline resins inthe group consisting of polyethylene resins such as a linear or branchedhigh density polyethylene, low density polyethylene, and ultra-highpolymer polyethylene; polypropylene resins such as linear or branchedhigh density polypropyrene and low density polypropyrene;ethylene-propylene copolymer, polymethylpentene, polybutene,polymethylbutene, and polymethylhexene; and the like can be given.

The blow-molded container of a multilayer laminate is preferable due toincreased pliability, impact resistance, heat resistance, and gasbarrier properties. Use of a gas barrier resin such as an ethylene-vinylalcohol copolymer, nylon, or the like as a material for another layer isparticularly preferable because of excellent gas barrier properties ofthe resulting blow-molded container. Either one layer or two or morelayers of the hydrogenated norbornene ring-open polymer and the otherthermoplastic resin may be provided.

There are no particular limitations to the constitution of themultilayer laminate inasmuch as such a multilayer laminate contains alayer of the hydrogenated norbornene ring-open polymer and a layer ofthe other thermoplastic resin. The following constitutions can be givenas specific examples. In the following constitutions, the layercontaining the hydrogenated ring-open polymer is indicated as “NB layer”and the other resin layers are indicated as “synthetic resin layer”.

(1) NB layer/synthetic resin layer(2) NB layer/synthetic resin layer/NB layer(3) Synthetic resin layer/NB layer/synthetic resin layer(4) NB layer/synthetic resin layer/synthetic resin layer/NB layer(5) NB layer/synthetic resin layer/NB layer/synthetic resin layer(6) NB layer/synthetic resin layer/NB layer/synthetic resin layer/NBlayer(7) Synthetic resin layer/synthetic resin layer/NB layer/synthetic resinlayer/synthetic resin layer(8) Synthetic resin layer/NB layer/synthetic resin layer/NBlayer/synthetic resin layer

The above layer constitutions are preferable examples but theblow-molded container of the present invention is not limited to these.An adhesive layer may optionally be provided between the layers.

In addition, the blow-molded container of the present invention may beprovided with a metallic foil such as an aluminum foil, an aluminumvapor deposition film, a laminate film of a metallic foil and asynthetic resin film, a layer which has a light blocking effect (shadinglayer) such as a synthetic resin film with a pigment incorporatedtherein. Among these shading layers, aluminum foil and an aluminum vapordeposition film, and the like have not only shading properties, but alsodamp-proofing properties, oil resistance, non-water-absorbingproperties. Therefore, these shading layers can provide a blow-moldedcontainer with the capability of storing chemicals and the like for along period of time. When co-extrusion is impossible, these shadinglayers may be added to the blow-molded container by lamination or thelike. As specific layer constitutions,

(1) NB layer/synthetic resin layer/shading layer,(2) NB layer/synthetic resin layer/shading layer/synthetic resin layer,(3) NB layer/shading layer,and the like can be given.

It is possible to employ other desired multilayer constitutionsaccording to the purpose of use, such as those having a larger number oflayers in addition to any one of the above layer combinations.

Although not particularly limited, the multilayer blow molded containeris generally fabricated by multilayer coextrusion blow molding orcoinjection stretching blow molding. It is also possible to multilayer ablow molded container after molding by a method of attaching a resinfilm using an adhesive, a method of bonding by fusing the resin film byheating or high frequency to a temperature above the melting point, amethod of applying a resin solution in an organic solvent and drying thecoating, and the like.

The blow molded container of the present invention has excellent steambarrier properties, heat resistance, transparency, and oil resistance,as well as high mechanical strength. The blow molded container of thepresent invention has an advantage of a wide processing temperaturerange due to the high thermal decomposition temperature of thehydrogenated norbornene ring-open polymer.

The blow molded container of the present invention has excellent steambarrier properties. It is possible to reduce the moisture permeability(g/(m²·24 h)) per 1 mm thickness of the barrel (side) of the blow moldedcontainer of the present invention measured based on JIS K7129 tousually 0.045 g/(m²·24 h) or less, preferably 0.035 g/(m²·24 h) or less,and more preferably 0.03 g/(m²·24 h) or less.

The blow molded container of the present invention has excellent oilresistance. The surface of the blow molded container of the presentinvention with a thickness of 1 mm is not whitened after immersing in ann-heptane test solution for 10 minutes.

The blow molded container of the present invention has excellenttransparency. The blow molded container of the present invention with athickness of 1 mm has a haze of usually 40% or less, preferably 30% orless, and more preferably 20% or less.

The blow molded container of the present invention which has thesecharacteristics can be used for a wide variety of applications in thefields of food industries, medical supplies, cosmetics, energy, opticalappliances, electric and electronic parts, telecommunications sector,vehicles, public welfare, toys, instruments for physics and chemistry,civil engineering and construction, and the like. Among these fields,the blow molded container of the present invention is particularlysuitable in the fields of food industries, medical supplies, cosmetics,and energy.

EXAMPLES

The present invention will be described below more specifically by wayof Examples and Comparative Examples, which are not intended to limitthe present invention. In the Examples and Comparative Examples,“part(s)” means “part(s) by weight” and “%” means “wt %” unlessotherwise indicated.

In the following Examples and Comparative Examples, various propertieswere measured by the following methods.

(A) Polymer Properties

(1) The weight average molecular weight (Mw) and the number averagemolecular weight (Mn) of the ring-open polymers were measured asstandard polystyrene-reduced values by gel permeation chromatography(GPC) using toluene as an eluant.

As the measuring device, GPC-8020 series instruments (DP8020, SD8022,AS8020, CO8020, and RI8020 manufactured by Tosoh Corp.) were used.

As the standard polystyrene, standard polystyrene having an Mw of atotal of eight points, 500, 2630, 10,200, 37,900, 96,400, 427,000,1,090,000, and 5,480,000, (manufactured by, Tosoh Corp.) was used.

The sample was prepared by dissolving the polymer to be analyzed intoluene to a concentration of 1 mg/ml and filtering through a cartridgefilter (made of polytetrafluoroethylene, pore size: 0.5 μm).

The molecular weight was measured by feeding a sample to two TSKgelGMHHR-H columns (manufactured by Tosoh Corp.) connected in series at aflow rate of 1.0 ml/min in an amount of 100 μml at a column temperatureof 40° C.

(2) The weight average molecular weight (Mw) and the number averagemolecular weight (Mn) of the hydrogenated ring-open polymers weremeasured as standard polystyrene-reduced values by gel permeationchromatography (GPC) using 1,2,4-trichlorobenzene as an eluant.

HLC8121GPC/HT (manufactured by Tosoh Corp.) was used as a measuringdevice.

As the standard polystyrene, standard polystyrene having an Mw of atotal of 16 points, 988, 2580, 5910, 9010, 18,000, 37,700, 95,900,18,6000, 351,000, 889,000, 1,050,000, 2,770,000, 5,110,000, 7,790,000,and 20,000,000 (manufactured by, Tosoh Corp.) was used.

The sample was prepared by dissolving the polymer to be analyzed in1,2,4-trichlorobenzene with heating at 140° C. to a concentration of 1mg/ml.

The molecular weight was measured by feeding a sample to three TSKgelGMHHR-H (20)HT columns (manufactured by Tosoh Corp.) connected in seriesat a flow rate of 1.0 ml/min in an amount of 300 μml at a columntemperature of 140° C.

(3) The degree of hydrogenation of the hydrogenated ring-open polymerwas determined by ¹H-NMR spectrum measurement using deuteriochloroformas a solvent.(4) The isomerization ratio was calculated using an equation, [33.0 ppmpeak integration value]/([31.8 ppm peak integration value]+[33.0 ppmpeak integration value])×100, wherein the peak integration value wasdetermined by ¹³C-NMR spectrum measurement using deuteriochloroform as asolvent.

The 31.8 ppm peak is a peak derived from cis-isomers of 2-norbornenerepeating units in the polymer and the 33.0 ppm peak is a peak derivedfrom trans-isomers of 2-norbornene repeating units in the polymer.

(5) Melting point was measured according to JIS K7121 using adifferential scanning calorimeter (DSC6220SII manufactured byNanoTechnology Inc.) after heating the sample to a temperature 30° C.higher than the melting point, cooling the sample to room temperature ata cooling rate of −10° C./min, and heating at a rate of 10° C./min.(6) Glass transition temperature was measured according to JIS K6911using a differential scanning calorimeter (DSC6220SII manufactured byNanoTechnology Inc.).

(B) Tube Sheet Properties

(1) Thickness of the sheet was measured using a micro gage.(2) Uneven thickness of the sheet was measured by applying five marks onthe film at 4 cm intervals in the direction (TD direction) vertical tothe flow direction of the sheet, applying 20 marks at 20 cm intervals inthe flow direction (MD direction) of the sheet starting from the firstfive marks, thereby applying 100 marks in total, measuring the filmthickness at 100 marked points, and calculating the standard deviationfrom the results. The smaller the value of the standard deviation, thesmaller the thickness unevenness of the sheet.(3) The steam barrier properties of the sheet was measured according toJIS K7129 (method A) using a moisture permeability tester (L80-5000type, manufactured by LYSSY) under conditions of a temperature of 50° C.and humidity of 90% RH. A small moisture permeability (g/(m²·24 h))indicates good steam barrier properties.(4) Modulus of elasticity of the sheet was measured according to ISO 527using a 1B shape test specimen obtained from the sheet at a tensilevelocity of 200 mm/min using Autograph (AGS-5kNH, manufactured byShimadzu Corp.). The test specimen was prepared so that its longitudinaldirection is the TD direction of the tube sheet.(5) Mechanical properties of the sheet were measured by inspecting astrain on the surface at the time of cracks according to ISO 527 using a1B shape test specimen prepared from the sheet at a tensile velocity of200 mm/min using Autograph (AGS-5kNH, manufactured by Shimadzu Corp.).The test specimen was prepared so that its longitudinal direction is theTD direction of the tube sheet.(6) Oil resistance of the sheet was evaluated by measuring the hazevalue before and after dipping a film prepared from the tube sheet insalad oil for one hour according to JIS-K7136 using a haze meter (NDH200A manufactured by Nihon Denshoku Industries Co., Ltd.), and dividingthe haze value of the untreated sheet with the haze value aftertreatment. The smaller the value, the worse the haze and the poorer theoil resistance.

(C) Properties of Blister-Molded Article

(1) Thickness of the film was measured using a micro gage.(2) The steam barrier properties was evaluated by measuring the moisturepermeability according to JIS K7129 (method A) using a moisturepermeability tester (L80-5000 type, manufactured by LYSSY) underconditions of a temperature of 40° C. and humidity of 90% RH andconditions of a temperature of 50° C. and humidity of 90% RH. A smallmoisture permeability (g/(m²·24 h)) indicates good steam barrierproperties.(3) The oil resistance was evaluated by applying salad oil (manufacturedby Nisshin Oillio Group, Ltd.) to the convex side (projected side) ofthe blister-molded articles, placing the sample in an oven heated at 40°C., and measuring the period of time elapsed before the outwardappearance of the sample changes. The longer the time elapsed before theoutward appearance of the blister-molded article changes, the better theoil resistance.(4) The blister moldability was evaluated by arbitrarily selecting tensheets of PTP

(number of pockets: five lengthwise, two in the lateral direction, totalten pockets), visually inspecting cylindrical areas of 100 PTPs to countthe number of cylindrical areas of which the bottom is inwardly dentedor the number of cylindrical areas of which the swelling is defective.The smaller the number of the PTPs having cylindrical areas of which theswelling is defective, the better the blister moldability.

If there is an uneven thickness in the pocket of a blister moldedarticle which is processed as a PTP, the bottom of the cylindrical upperpart of the pocket may inwardly dent or the cylindrical part mayinadequately expand. Blister moldability can be evaluated by evaluatingsuch a dent and inadequate expansion.

(D) Properties of Multilayer Laminate

(1) Thickness of the film was measured using a micro gage.(2) The impact resistance was evaluated by preparing bags (n=100) with asize of 20 cm×20 cm, sealing the four sides of the bags with heat,putting brine in the bags, and dropping the bags from a height of 3 m,observing the presence or absence of cracks after dropping, and countingthe number of cracked bags. The smaller the number of cracks, the betterthe impact resistance.(3) The steam barrier properties were evaluated by measuring moisturepermeability according to JIS K7129 (method A) using a moisturepermeability tester (L80-5000 type, manufactured by LYSSY) underconditions of a temperature of 50° C. and humidity of 90% RH. A smallmoisture permeability (g·(m²·24 h)) indicates good steam barrierproperties.(4) The oil resistance was evaluated by cutting a 5 cm square from thefilm, dipping the sample in salad oil (manufactured by Nisshin OillioGroup, Ltd.) for 30 seconds, and placing the sample in an oven heated at40° C., and measuring the period of time elapsed before the outwardappearance of the sample changes. The longer the time elapsed before theoutward appearance of the film changes, the better the oil resistance.(5) The gas barrier properties were evaluated by boiling the film inboiling water for 30 minutes and measuring the gas barrier propertiesbefore and after boiling according to MS K7126 (method B) underconditions of a temperature of 23° C. and humidity of 0% RH using anoxygen permeability tester (OPT-5000 type, manufactured by LYSSY). Asmall oxygen permeability (cm³·m⁻²·day⁻¹·atm⁻¹ indicates good steambarrier properties.

(E) Properties of Blow-Molded Container

(1) Blow moldability was evaluated by measuring the thickness t of thebody of the blow-molded container by applying a probe of an ultrasonicthickness meter (manufactured by KARL DEUTSCH) to the side of theblow-molded container body. Specifically, the blow-molded container wasplaced on a horizontal plane and the thickness was measured at 100points starting from a point 10 mm from the horizontal plane at 5 mmintervals. The standard deviation (σ) was calculated.(2) The steam barrier properties were evaluated by measuring moisturepermeability according to JIS K7129 (method A) using a moisturepermeability tester (L80-5000 type, manufactured by LYSSY) underconditions of a temperature of 40° C. and humidity of 90% RH. A smallmoisture permeability (g/(m²·24 h)) indicates good steam barrierproperties. The test for steam barrier properties was carried out usinga plate-like sample prepared from the blow-molded container.(3) A falling-weight impact resistance was evaluated by filling theblow-molded containers with brine in an amount equivalent to 90% of thetotal volume, dropping the container from a height (from the ground tothe bottom of the container) of 1 m, and observing the conditions of thecontainers after falling. The number of containers with no cracks orleaks among 30 tested containers was counted.(4) The normal heptane impregnation test was carried out as an oilresistance evaluation test. 2.5 l of n-heptane (manufactured by WakoPure Chemical Industries, Ltd.) was added to a 3 l glass beaker. Thesample containers were immersed in n-heptane in the glass beaker. Thecondition of the sample container surface (whether the surface waswhitened or not and cracked or not) was observed after 10 minutes ofimmersion.(5) Haze (%) was measured by preparing samples with a thickness of 1 mmby cutting the blow-molded container and measuring the samples using ahaze meter (“NDH2000” manufactured by Nippon Denshoku Co., Ltd.).

(F) Properties of Molding Material

(1) The amount of organic substances discharged was measured by washing5 g of the molding material sample with a large amount of ultra purewater in a clean room (class 1000), placing the sample in a glass samplecontainer completely free from moisture and organic substances adheringto the surface, heating the sample container at 80° C. for 60 minutes,and measuring gases discharged from the sample container by heatdesorption gas chromatography mass spectrometer (TDS-GC-MS manufacturedby Agilent Technologies).(2) The heat resistance of the container was confirmed by allowing awafer carrier produced from the molding material to stand at atemperature of 105° C. for 30 minutes and observing whether or not thewafer carrier was deformed. The sample was rated as “Good” if the waferwas not deformed and as “Bad” if the wafer was deformed.(3) The content of transition metals was measured using an inductivelycoupled plasma optical emission spectrometry (IRIS Advantage/SSEA,manufactured by Nippon Jarrell-Ash Co. Ltd.).(4) In measuring an increased amount of foreign matter, a new 8-inchbear silicon wafer purchased packed in a polypropylene wafer shipper wasimmersed in a 4.5 wt % solution of hydrofluoric acid at 25° C. for oneminute to remove a thin silicon oxide film in a clean room (class 1000),and then immersed in a 50:1 (by vol) mixture of 98% concentratedsulfuric acid and a 30% hydrogen peroxide aqueous solution at 110° C.for 10 minutes. Next, after removing organic substances by immersing inconcentrated sulfuric acid at 65° C. for 10 minutes and washing away theacid with a large amount of ultra-pure water and completely removingwater by a centrifugal separator, the number of foreign matter particleson the dried wafer was counted using a foreign matter detector (SurfscanSP1 manufactured by KLA-Tencor corp.). After the wafer was inserted inand removed from the molded wafer carrier 50 times, the number offoreign matter particles on the wafer was counted again. The increasedamount of foreign matter was evaluated by the difference of the numberof foreign matter particles before and after the test.

Example 1 Ring-Opening Polymerization

A reactor was charged with 500 parts by weight of dehydratedcyclohexane, 0.55 parts by weight of 1-hexene, 0.30 parts by weight ofdiisopropyl ether, 0.20 parts by weight of triisobutylaluminum, and0.075 parts by weight of isobutyl alcohol at room temperature under anitrogen atmosphere. While maintaining the temperature at 55° C., 250parts by weight of 2-norbornene and 15 parts by weight a 1.0 wt %solution of tungsten hexachloride in toluene were continuously added intwo hours to polymerize the monomers. The weight average molecularweight (Mw) of the resulting ring-open polymer (1) was 83,000, and themolecular weight distribution (Mw/Mn) was 1.8.

(Hydrogenation Reaction)

The polymerization reaction solution containing the ring-open polymer(1) obtained above was transferred to a pressure resistant hydrogenationreactor. After the addition of 0.5 parts by weight of a nickel catalystsupported by diatomaceous earth (T8400, nickel support rate: 58 wt %,manufactured by Nissan-Süd-Chemie), the hydrogenation reaction wascarried out at 160° C. under a hydrogen pressure of 4.5 MPa for sixhours. The reaction solution was filtered through a stainless steel wiremesh filter, in which diatomaceous earth was used as a filtrationadjuvant, to remove the catalyst.

The filtrate was poured into 3000 parts by weight of isopropyl alcoholwhile stirring to precipitate the hydrogenated product. After washingwith 500 parts by weight of acetone, the hydrogenated product was driedin a vacuum dryer at 100° C. under 0.13×10³ Pa for 48 hours to obtain190 parts by weight of a hydrogenated ring-open polymer (1).

(Properties of Polymer)

The degree of hydrogenation of the resulting hydrogenated ring-openpolymer (1) was 99.9%, the weight average molecular weight (Mw) was82,200, the molecular weight distribution (Mw/Mn) was 2.9, theisomerization ratio was 5%, and the melting point was 140° C.

(Preparation of Resin Composition)

0.1 part by weight oftetrakis[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane(Irganox 1010 manufactured by Ciba Geigy, hereinafter referred to as“Antioxidant A”) was added to 100 parts by weight of a hydrogenatedring-open polymer (1) and the mixture was kneaded using a twin-screwkneader (TEM35 manufactured by Toshiba Machine Co., Ltd.) to obtainpellets.

(Preparation of Resin Sheet)

The pellets were pressed by a vacuum heat-press apparatus (manufacturedby Imoto Factory Co., Ltd.) at a die temperature of 150° C. under apressure of 8 MPa for five minutes, using a mold die with a thickness of1 mm, a length of 200 mm, and a width of 100 mm, with one side beingmirror plane processed, and cooled to room temperature at a cooling rateof 0.5° C./min to obtain a resin sheet (1).

Example 2 Hydrogenation Reaction

A polymerization reaction solution containing the ring-open polymer (1)obtained in the same manner as in Example 1 was transferred to apressure resistant hydrogenation reactor. After the addition of 1.0 partby weight of a nickel catalyst supported by diatomaceous earth (T8400,nickel support rate: 58 wt %, manufactured by Nissan-Süd-Chemie), thehydrogenation reaction was carried out at 165° C. under a hydrogenpressure of 4.5 MPa for six hours. The reaction solution was filteredthrough a stainless steel wire mesh filter, in which diatomaceous earthwas used as a filtration adjuvant, to remove the catalyst. The filtratewas poured into 3000 parts by weight of isopropyl alcohol while stirringto precipitate the hydrogenated product. After washing with 500 parts byweight of acetone, the hydrogenated product was dried in a vacuum dryerat 100° C. under 0.13×10³ Pa for 48 hours to obtain 190 parts by weightof a hydrogenated ring-open polymer (2).

(Properties of Polymer)

The degree of hydrogenation of the resulting hydrogenated ring-openpolymer (2) was 99.9%, the weight average molecular weight (Mw) was82,000, the molecular weight distribution (Mw/Mn) was 2.8, theisomerization ratio was 15%, and the melting point was 134° C.

(Preparation of Resin Composition)

0.1 part by weight of Antioxidant A was added to 100 parts by weight ofthe hydrogenated ring-open polymer (2) and the mixture was kneaded usinga twin-screw kneader (TEM35 manufactured by Toshiba Machine Co., Ltd.)to obtain a pelletized resin composition.

(Preparation of Resin Sheet)

The pellets were pressed by a vacuum heat-press apparatus (manufacturedby Imoto Factory Co., Ltd.) at a die temperature of 145° C. under apressure of 8 MPa for five minutes, using a mold die with a thickness of1 mm, a length of 200 mm, and a width of 100 mm, with one side beingmirror plane processed, and cooled to room temperature at a cooling rateof 0.5° C./min to obtain a resin sheet (2).

Example 3 Hydrogenation Reaction

A polymerization reaction solution containing the ring-open polymer (1)obtained in the same manner as in Example 1 was transferred to apressure resistant hydrogenation reactor. After the addition of 4 partsby weight of a nickel catalyst supported by diatomaceous earth (T8400,nickel support rate: 58 wt %, manufactured by Nissan-Süd-Chemie), thehydrogenation reaction was carried out at 180° C. under a hydrogenpressure of 4.5 MPa for six hours. The reaction solution was filteredthrough a stainless steel wire mesh filter, in which diatomaceous earthwas used as a filtration adjuvant, to remove the catalyst. The filtratewas poured into 3000 parts by weight of isopropyl alcohol while stirringto precipitate the hydrogenated product. After washing with 500 parts byweight of acetone, the hydrogenated product was dried in a vacuum dryerat 100° C. under 0.13×10³ Pa for 48 hours to obtain 190 parts by weightof a hydrogenated ring-open polymer (3).

(Properties of Polymer)

The degree of hydrogenation of the resulting ring-open polymer (3) was99.9%, the weight average molecular weight (Mw) was 81,600, themolecular weight distribution (Mw/Mn) was 2.8, the isomerization ratiowas 35%, and the melting point was 125° C.

(Preparation of Resin Composition)

0.1 part by weight of Antioxidant A was added to 100 parts by weight ofthe hydrogenated ring-open polymer (3) and the mixture was kneaded usinga twin-screw kneader (TEM35 manufactured by Toshiba Machine Co., Ltd.)to obtain a pelletized resin composition.

(Preparation of Resin Sheet)

The pellets were pressed by a vacuum heat-press apparatus (manufacturedby Imoto Factory Co., Ltd.) at a die temperature of 135° C. under apressure of 8 MPa for five minutes, using a mold die with a thickness of1 mm, a length of 200 mm, and a width of 100 mm, with one side beingmirror plane processed, and cooled to room temperature at a cooling rateof 0.5° C./min to obtain a resin sheet (3).

Example 4 Ring-Opening Polymerization

A polymerization reaction was carried out in the same manner as inExample 1 except for using 0.20 parts by weight of 1-hexene, 0.40 partsby weight of diisopropyl ether, 0.27 parts by weight oftriisobutylaluminum, 0.10 part by weight of isobutyl alcohol, and 20parts by weight of a 1.0% tungsten hexachloride solution in toluene, toobtain a reaction solution containing a ring-open polymer (2). Theweight average molecular weight (Mw) of the resulting ring-open polymer(2) was 153,000, and the molecular weight distribution (Mw/Mn) was 3.0.

(Hydrogenation Reaction)

The reaction solution containing the ring-open polymer (2) obtainedabove was transferred to a pressure resistant hydrogenation reactor.After the addition of 2 parts by weight of a nickel catalyst supportedby diatomaceous earth (T8400, nickel support rate: 58 wt %, manufacturedby Nissan-Süd-Chemie), the hydrogenation reaction was carried out at160° C. under a hydrogen pressure of 4.5 MPa for six hours. The reactionsolution was filtered through a stainless steel wire mesh filter, inwhich diatomaceous earth was used as a filtration adjuvant, to removethe catalyst. The filtrate was poured into 3000 parts by weight ofisopropyl alcohol while stirring to precipitate the hydrogenatedproduct. After washing with 500 parts by weight of acetone, thehydrogenated product was dried in a vacuum dryer at 100° C. under0.13×10³ Pa for 48 hours to obtain 190 parts by weight of a hydrogenatedring-open polymer (4).

(Properties of Polymer)

The degree of hydrogenation of the resulting hydrogenated ring-openpolymer (4) was 99.9%, the weight average molecular weight (Mw) was150,500, the molecular weight distribution (Mw/Mn) was 4.0, theisomerization ratio was 9%, and the melting point was 136° C.

(Preparation of Resin Composition)

0.1 part by weight of Antioxidant A was added to 100 parts by weight ofthe hydrogenated ring-open polymer (4) and the mixture was kneaded usinga twin-screw kneader (TEM35 manufactured by Toshiba Machine Co., Ltd.)to obtain a pelletized resin composition.

(Preparation of Resin Sheet)

The pellets were pressed by a vacuum heat-press apparatus (manufacturedby Imoto Factory Co., Ltd.) at a die temperature of 150° C. under apressure of 8 MPa for five minutes, using a mold die with a thickness of1 mm, a length of 200 mm, and a width of 100 mm, with one side beingmirror plane processed, and cooled to room temperature at a cooling rateof 0.5° C./min to obtain a resin sheet (4).

Example 5 Ring-Opening Polymerization

A solution containing a ring-open polymer (3) was obtained in the samemanner as in Example 1 except for using 0.10 part by weight of 1-hexene,0.40 parts by weight of diisopropyl ether, 0.27 parts by weight oftriisobutylaluminum, 0.10 part by weight of isobutyl alcohol, and 20parts by weight of a 1.0% tungsten hexachloride solution in toluene.

The weight average molecular weight (Mw) of the resulting ring-openpolymer (3) was 189,500, and the molecular weight distribution (Mw/Mn)was 3.3.

(Hydrogenation Reaction)

The reaction solution containing the ring-open polymer (3) obtainedabove was transferred to a pressure resistant hydrogenation reactor.After the addition of 1 part by weight of a nickel catalyst supported bydiatomaceous earth (T8400, nickel support rate: 58 wt %, manufactured byNissan-Süd-Chemie), the hydrogenation reaction was carried out at 160°C. under a hydrogen pressure of 4.5 MPa for six hours. The reactionsolution was filtered through a stainless steel wire mesh filter, inwhich diatomaceous earth was used as a filtration adjuvant, to removethe catalyst. The filtrate was poured into 3000 parts by weight ofisopropyl alcohol while stirring to precipitate the hydrogenatedproduct. After washing with 500 parts by weight of acetone, thehydrogenated product was dried in a vacuum dryer at 100° C. under0.13×10³ Pa for 48 hours to obtain 190 parts by weight of a hydrogenatedring-open polymer (5).

(Properties of Polymer)

The degree of hydrogenation of the resulting hydrogenated ring-openpolymer (5) was 99.9%, the weight average molecular weight (Mw) was185,000, the molecular weight distribution (Mw/Mn) was 4.4, theisomerization ratio was 10%, and the melting point was 136° C.

(Preparation of Resin Composition)

0.1 part by weight of Antioxidant A was added to 100 parts by weight ofthe hydrogenated ring-open polymer (5) and the mixture was kneaded usinga twin-screw kneader (TEM35 manufactured by Toshiba Machine Co., Ltd.)to obtain a pelletized resin composition.

(Preparation of Resin Sheet)

The pellets were pressed by a vacuum heat-press apparatus (manufacturedby Imoto Factory Co., Ltd.) at a die temperature of 150° C. under apressure of 8 MPa for five minutes, using a mold die with a thickness of1 mm, a length of 200 mm, and a width of 100 mm, with one side beingmirror plane processed, and cooled to room temperature at a cooling rateof 0.5° C./min to obtain a resin sheet (5).

Comparative Example 1 Ring-Opening Polymerization

A reaction solution containing a norbornene ring-open polymer (4) wasobtained in the same manner as in Example 1, except for using 1.3 partsby weight of 1-hexene. The weight average molecular weight (Mw) of theresulting ring-open polymer (4) was 39,800, and the molecular weightdistribution (Mw/Mn) was 1.7.

(Hydrogenation Reaction)

The reaction solution containing the ring-open polymer (4) obtainedabove was transferred to a pressure resistant hydrogenation reactor.After the addition of 0.5 parts by weight of a nickel catalyst supportedby diatomaceous earth (T8400, nickel support rate: 58 wt %, manufacturedby Nissan-Süd-Chemie), the hydrogenation reaction was carried out at160° C. under a hydrogen pressure of 4.5 MPa for six hours. The solutionwas filtered through a stainless steel wire mesh filter, in whichdiatomaceous earth was used as a filtration adjuvant, to remove thecatalyst. The filtrate was poured into 3000 parts by weight of isopropylalcohol while stirring to precipitate the hydrogenated product. Afterwashing with 500 parts by weight of acetone, the hydrogenated productwas dried in a vacuum dryer at 100° C. under 0.13×10³ Pa for 48 hours toobtain 190 parts by weight of a hydrogenated ring-open polymer (6).

(Properties of Polymer)

The degree of hydrogenation of the resulting hydrogenated ring-openpolymer (6) was 99.9%, the weight average molecular weight (Mw) was38,200, the molecular weight distribution (Mw/Mn) was 2.6, theisomerization ratio was 6%, and the melting point was 142° C.

(Preparation of Resin Composition)

0.1 part by weight of Antioxidant A was added to 100 parts by weight ofthe hydrogenated ring-open polymer (6) and the mixture was kneaded usinga twin-screw kneader (TEM35 manufactured by Toshiba Machine Co., Ltd.)to obtain a pelletized resin composition.

(Preparation of Resin Sheet)

The pellets were pressed by a vacuum heat-press apparatus (manufacturedby Imoto Factory Co., Ltd.) at a die temperature of 150° C. under apressure of 8 MPa for five minutes, using a mold die with a thickness of1 mm, a length of 200 mm, and a width of 100 mm, with one side beingmirror plane processed, and cooled to room temperature at a cooling rateof 0.5° C./min to obtain a resin sheet (6).

Comparative Example 2 Ring-Opening Polymerization

An autoclave equipped with a stirrer was charged with 1.1 parts byweight of tungsten (phenylimide)tetrachloride diethyl ether and 18.5parts by weight of cyclohexane. A solution of 0.87 parts by weight ofdiethylaluminum ethoxide in 9.26 parts by weight of hexane was furtheradded and the mixture was stirred for 30 minutes at room temperature.After the addition of 139 parts by weight of dicyclopentadiene and 0.33parts by weight of 1-hexene, the polymerization reaction was carried outat 50° C. for three hours to obtain a reaction solution containing aring-open polymer (5).

The weight average molecular weight (Mw) of the resulting ring-openpolymer (5) was 78,000, and the molecular weight distribution (Mw/Mn)was 3.5.

(Hydrogenation Reaction)

A hydrogenation catalyst solution containing 0.87 parts by weight ofbis(tricyclohexylphosphine)benzylidyne ruthenium (IV) dichloride and20.4 parts by weight of ethyl vinyl ether dissolved in 650 parts byweight of cyclohexane was added to the resulting polymer solution, andthe hydrogenation reaction was carried out at 160° C. under a hydrogenpressure of 1.0 MPa for 20 hours. The reaction solution was poured intoa large amount of isopropanol to cause the polymer to completelyprecipitate. The precipitate was collected by filtration. After washingwith 500 parts by weight of acetone, the precipitate was dried in avacuum dryer at 100° C. under 0.13×10³ Pa for 48 hours to obtain 130parts by weight of a hydrogenated ring-open polymer (7).

Since the hydrogenated ring-open polymer (7) was insoluble in the GPCsolvent, the molecular weight could not be measured. The melting pointwas 273° C.

(Preparation of Resin Composition)

0.1 part by weight of Antioxidant A was added to 100 parts by weight ofthe hydrogenated ring-open polymer (7) and the mixture was kneaded usinga twin-screw kneader (TEM35 manufactured by Toshiba Machine Co., Ltd.)to obtain a pelletized resin composition.

(Preparation of Resin Sheet)

The pellets were pressed by a vacuum heat-press apparatus (manufacturedby Imoto Factory Co., Ltd.) at a die temperature of 280° C. under apressure of 8 MPa for five minutes, using a mold die with a thickness of1 mm, a length of 200 mm, and a width of 100 mm, with one side beingmirror plane processed, and cooled to room temperature at a cooling rateof 0.5° C./min to obtain a resin sheet (7).

Reference Example 1 Ring-Opening Polymerization

An autoclave equipped with a stirrer was charged with 37.5 parts byweight of a 70 wt % norbornene solution in toluene, 0.052 parts byweight of 1-hexene, and 49.3 parts by weight of cyclohexane, and themixture was stirred. Then, a solution containing 0.023 parts by weightof 2,6-diisopropylphenylimide neophylidene molybdenum (VI)bis(t-butoxide) and 0.016 parts by weight of trimethylphosphine in 8.6parts by weight of toluene were added, and the reaction was carried outat 30° C. for one hour. 0.40 parts by weight of benzaldehyde was addedto the reaction mixture to obtain a reaction solution containing aring-open polymer (6).

The weight average molecular weight (Mw) of the resulting ring-openpolymer (6) was 65,000, and the molecular weight distribution (Mw/Mn)was 1.1.

(Hydrogenation Reaction)

The reaction solution containing the ring-open polymer (6) obtainedabove was transferred to a pressure resistant hydrogenation reactor.After the addition of 5.25 parts by weight of Pd/CaCO₃ (amount of Pd: 5wt %, manufactured by Strem Chemicals, Inc.) as a catalyst, thehydrogenation reaction was carried out at 100° C. under a hydrogenpressure of 3.5 MPa for 48 hours. The reaction solution was filteredthrough a stainless steel wire mesh filter, in which diatomaceous earthwas used as a filtration adjuvant, to remove the catalyst. The filtratewas poured into 3000 parts by weight of isopropyl alcohol while stirringto precipitate the hydrogenated product. After washing with 500 parts byweight of acetone, the hydrogenated product was dried in a vacuum dryerat 100° C. under 0.13×10³ Pa for 48 hours to obtain 190 parts by weightof a hydrogenated ring-open polymer (8).

(Properties of Polymer)

The degree of hydrogenation of the resulting hydrogenated ring-openpolymer (8) was 99.75%, the weight average molecular weight (Mw) was64,200, the molecular weight distribution (Mw/Mn) was 1.3, theisomerization ratio was 0%, and the melting point was 143° C.

(Preparation of Resin Composition)

0.1 part by weight of Antioxidant A was added to 100 parts by weight ofthe hydrogenated ring-open polymer (8) and the mixture was kneaded usinga twin-screw kneader (TEM35 manufactured by Toshiba Machine Co., Ltd.)to obtain a pelletized resin composition.

(Preparation of Resin Sheet)

The pellets were pressed by a vacuum heat-press apparatus (manufacturedby Imoto Factory Co., Ltd.) at a die temperature of 150° C. under apressure of 8 MPa for five minutes, using a mold die with a thickness of1 mm, a length of 200 mm, and a width of 100 mm, with one side beingmirror plane processed, and cooled to room temperature at a cooling rateof 0.5° C./min to obtain a resin sheet (8).

Comparative Example 3 Ring-Opening Polymerization and HydrogenationReaction

Polymerization was carried out in the same manner as in Example 1,except that 200 parts by weight of methyltetracyclododecene (MTD) and 50parts by weight of dicyclopentadiene (DCP) were used instead of2-norbornene, and the amount of 1-hexene used was 0.70 parts by weight.

The weight average molecular weight (Mw) of the resulting ring-openpolymer (7) was 56,000, and the molecular weight distribution (Mw/Mn)was 2.0.

The hydrogenation reaction was carried out in the same manner as inExample 3 to obtain a hydrogenated ring-open polymer (9).

(Properties of Polymer)

The degree of hydrogenation of the resulting hydrogenated ring-openpolymer (9) was 99.9%, the weight average molecular weight (Mw) was55,000, the molecular weight distribution (Mw/Mn) was 3.1, the glasstransition temperature was 140° C., and a melting point was notobserved.

(Preparation of Resin Composition)

0.1 part by weight of Antioxidant A was added to 100 parts by weight ofthe hydrogenated ring-open polymer (9) and the mixture was kneaded usinga twin-screw kneader (TEM35 manufactured by Toshiba Machine Co., Ltd.)to obtain a pelletized resin composition.

(Preparation of Resin Sheet)

The pellets were pressed by a vacuum heat-press apparatus (manufacturedby Imoto Factory Co., Ltd.) at a die temperature of 220° C. under apressure of 8 MPa for five minutes, using a mold die with a thickness of1 mm, a length of 200 mm, and a width of 100 mm, with one side beingmirror plane processed, and cooled to room temperature at a cooling rateof 0.5° C./min to obtain a resin sheet (9).

Comparative Example 4 Ring-Opening Polymerization and HydrogenationReaction

Polymerization was carried out in the same manner as in Example 5,except that 0.06 parts by weight of 1-hexene was used.

The weight average molecular weight (Mw) of the resulting ring-openpolymer (8) was 310,000, and the molecular weight distribution (Mw/Mn)was 3.2. The hydrogenation reaction was carried out in the same manneras in Example 1 to obtain a hydrogenated norbornene ring-open polymer(10).

(Properties of Polymer)

The degree of hydrogenation of the resulting hydrogenated ring-openpolymer (10) was 99.0%, the weight average molecular weight (Mw) was300,200, the molecular weight distribution (Mw/Mn) was 4.5, theisomerization ratio was 6%, and the melting point was 140° C.

(Preparation of Resin Composition)

0.1 part by weight of Antioxidant A was added to 100 parts by weight ofthe hydrogenated ring-open polymer (10) and the mixture was kneadedusing a twin-screw kneader (TEM35 manufactured by Toshiba Machine Co.,Ltd.) to obtain a pelletized resin composition.

(Preparation of Resin Sheet)

The pellets were pressed by a vacuum heat-press apparatus (manufacturedby Imoto Factory Co., Ltd.) at a die temperature of 150° C. under apressure of 8 MPa for five minutes, using a mold die with a thickness of1 mm, a length of 200 mm, and a width of 100 mm, with one side beingmirror plane processed, and cooled to room temperature at a cooling rateof 0.5° C./min to obtain a resin sheet (10).

(Solubility Evaluation Test (c-Hex Solubility))

Solubility in cyclohexane was evaluated using the hydrogenated ring-openpolymers (1) to (10). The solubility was judged by preparing acyclohexane solution of the ring-open polymer with a concentration of20% at 70° C. and cooling the solution, while observing the temperatureat which the polymer is deposited with the naked eye. The results areshown in Table 2.

(Processability Evaluation Test (1))

Processability was evaluated using the hydrogenated ring-open polymers(1) to (10). The processability was evaluated by measuring the thicknessof monolayer films (C1) (thickness: 100 μm) obtained by molding thepellets of the hydrogenated ring-open polymer (1) to (10) by T-diemolding using a hanger manifold T-die film melt extruding press machine(stationary type manufactured by GSI Creos Corp.) equipped with a screwhaving a screw diameter of 20 mm, a compression ratio of 2.5 or 3.1, andL/D=30 under the following conditions. The results are shown in Table 2.

Specifically, the film thickness was measured at 100 points in the MDdirection at intervals of 2.5 m using a micro gage to calculate thestandard deviation (a).

<Molding Conditions> Die lip: 0.8 mm

Molten resin temperature: Tm of resin+40° C. (resin without a meltingpoint: Tg+100° C.)

Width of T-die: 300 mm

T-die temperature: Tm of resin+50° C. (resin without a melting point:Tg+110° C.)Cooling roll: Tm of resin−20° C. (resin without a melting point: Tg−15°C.)Casting roll: Tm of resin−10° C. (resin without a melting point: Tg−5°C.)Sheet roll-up rate: 2.5 m/minScrew compression ratio: a screw with a compression ratio of 2.5 wasused for resins having no melting point, and a screw with a compressionratio of 3.1 was used for other resins.

(Processability Evaluation Test (2))

The processability was evaluated by the film thickness variation whenmonolayer films (C1) (thickness: 100 μm) were continuously produced foreight hours and the time before a die line was generated (die linegeneration time) using the same extruding press machine as used in theprocessability evaluation test (1), of which the conditions were set sothat the resin pressure at the die portion was 3 MPa on average.

The same process conditions as in the processability evaluation test (1)were employed, except that the molten resin temperature and the T-dietemperature shown in the following Table 1 were used when processing thehydrogenated ring-open polymers (1) to (10).

TABLE 1 Hydrogenated ring- Molten resin temperature T-die temperatureopen polymer (° C.) (° C.) 1 180 190 2 175 185 3 165 175 4 200 210 5 210220 6 170 180 7 310 320 8 180 190 9 250 260 10 260 270

Specifically, at every one hour after the start of film formation, thefilm thickness was measured at 10 points in the MD direction atintervals of 2.5 m (total of 80 points) using a micro gage to calculatethe standard deviation. The time required for the die line to begenerated from the start of film formation was measured by visuallyjudging the occurrence of the die line.

(Measurement of Tensile Breaking Elongation)

Tensile breaking elongation was measured for each of the resin sheets(1) to (10) obtained in the above. Tensile breaking elongation wasmeasured according to ISO 527 at a tensile velocity of 200 mm/min usingAutograph (AGS-5kNH, manufactured by Shimadzu Corp.).

The measurement results are shown in Table 2.

(Evaluation Test of Steam Barrier Properties)

Moisture permeability of each of the sheets (1) to (10) obtained abovewas evaluated. The moisture permeability was measured according to JISK7129 (method A) using a moisture permeability tester (L80-5000 type,manufactured by LYSSY) under conditions of a temperature of 40° C. andhumidity of 90% RH. The measurement results are shown in Table 2. Asmall moisture permeability (g/(m²·24 h)) indicates good steam barrierproperties.

(Evaluation of Oil Resistance)

Oil resistance of each of the sheets (1) to (10) obtained above wasevaluated. Critical stress to salad oil (manufactured by Nisshin OillioGroup, Ltd.) was used for evaluation of the oil resistance. Afterapplying salad oil to the surface of a test specimen with dimensions of10 mm×100 mm×1 mm prepared by heat-pressing, the test specimen wassecured for one hour to a curvature of an aluminum jig made by cuttingan elliptic cylinder with a height of 10 mm, a major ellipse axis of 200mm and a minor ellipse axis of 80 mm into four equal divisions, toobserve whether or not cracks were produced in the test specimen. Alltest specimens were secured at fixed positions. For a test specimen inwhich the cracks were generated, the crack generating positions weremeasured taking the end of the test specimen on the low curvature sideat the time of securing as the starting point. The results are shown inTable 2.

TABLE 2 Processability Processability c-Hex test (1) test (2) TensileHydrogenated solubility Standard Standard Die line breaking Moisturering-open (depositing Resin deviation deviation generation elongationpermeability Oil polymer temperature) sheet (σ) (σ) time (%) (g/(m² · 24h)) resistance Example 1 1 65° C. 1 5 μm 3 μm ≧15 hrs 30 0.23 No cracks2 2 60° C. 2 6 μm 4 μm ≧15 hrs 30 0.25 No cracks 3 3 40° C. 3 6 μm 4 μm≧15 hrs 35 0.30 No cracks 4 4 62° C. 4 7 μm 5 μm  10 hrs 35 0.28 Nocracks 5 5 62° C. 5 8 μm 5 μm  10 hrs 25 0.31 No cracks Comparative 1 669° C. 6 10 μm  7 μm ≧15 hrs 8 0.24 Cracks at Example 75 mm 2 7 Not 7 10μm  8 μm    2 hrs 15 0.78 No cracks dissolved Reference 1 8 69° C. 8 18μm  10 μm   13 hrs 25 0.23 No cracks Example Comparative 3 9 ≦25° C.  95 μm 4 μm    6 hrs 40 0.98 Cracks at Example 45 mm 4 10 35° C. 10 15 μm 7 μm    3 hrs 25 0.28 No cracks

As shown in Table 2, the hydrogenated ring-open polymers (1) to (5) ofExamples 1 to 5 showed excellent solubility in cyclohexane (c-Hex) andprocessability. The resin sheets (1) to (5) of Examples 1 to 5 exhibitedexcellent mechanical properties as indicated by the tensile breakingelongation of 25% or more, and excellent steam barrier properties asindicated by the moisture permeability of 0.31 g/(m²·24 h) or less.Furthermore, the resin sheets (1) to (5) of Examples 1 to 5 exhibitedexcellent oil resistance.

On the other hand, the hydrogenated ring-open polymers (6), (7), and (8)of Comparative Examples 1 and 2 and Reference Example 1 showed poorsolubility in cyclohexane as compared with the hydrogenated ring-openpolymers of the Examples.

In addition, the hydrogenated ring-open polymers (6), (7), (8), and (10)of Comparative Examples 1, 2, and 4 and Reference Example 1 showed poorprocessability as compared with the hydrogenated ring-open polymers ofthe Examples.

Furthermore, the hydrogenated ring-open polymers (6), (7), (8), and (10)of Comparative Examples 1, 2, and 4 and Reference Example 1 had tensilebreaking elongation of 25% or less, showing the same or inferiormechanical properties as compared with the hydrogenated ring-openpolymers of the Examples. The moisture permeability of the resin sheets(7) and (9) of Comparative Examples 2 and 3 was 0.78 g/(m²·24 h) ormore, indicating poor steam barrier properties of these resin sheets ascompared with the resin sheets of the Examples. Furthermore, the resinsheets (6) and (9) of Comparative Examples 1 and 3 exhibited poor oilresistance.

Based on the above results, the hydrogenated ring-open polymers andsheets of Examples 1 to 5 can be regarded as excellent in allperformance properties, including steam barrier properties, heatresistance, oil resistance, mechanical properties, transparency, andprocessability demanded in recent years in the fields of informationprocessing, food industries, medical supplies, engineering works, andthe like.

Example 6 Ring-Opening Copolymerization

A reactor was charged with 500 parts by weight of dehydratedcyclohexane, 0.40 parts by weight of 1-hexene, 0.31 parts by weight ofdiisopropyl ether, 0.20 parts by weight of triisobutylaluminum, and 0.08parts by weight of isobutyl alcohol at room temperature under a nitrogenatmosphere. While maintaining the temperature at 55° C., 245 parts byweight of 2-norbornene, 5 parts by weight of methylnorbornene, and 15parts by weight of a 1.0 wt % solution of tungsten hexachloride intoluene were continuously added in two hours to polymerize the monomers.The polymerization conversion rate was about 100%.

The weight average molecular weight (Mw) of the resulting ring-openpolymer (9) was 103,000, and the molecular weight distribution (Mw/Mn)was 1.9.

(Hydrogenation Reaction)

The polymerization reaction solution obtained above was transferred to apressure resistant hydrogenation reactor. After the addition of 0.5parts by weight of a nickel catalyst supported by diatomaceous earth(T8400, nickel support rate: 58 wt %, manufactured byNissan-Sud-Chemie), the hydrogenation reaction was carried out at 160°C. under a hydrogen pressure of 4.5 MPa for six hours. The reactionsolution was filtered through a stainless steel wire mesh filter, inwhich diatomaceous earth was used as a filtration adjuvant, to removethe catalyst. The filtrate was poured into 3000 parts by weight ofisopropyl alcohol while stirring to precipitate the hydrogenatedproduct. After washing with 500 parts by weight of acetone, thehydrogenated product was dried in a vacuum dryer at 100° C. under0.13×10³ Pa for 48 hours to obtain 190 parts by weight of a hydrogenatedring-open polymer (11).

(Properties of Polymer)

The degree of hydrogenation of the resulting hydrogenated ring-openpolymer (11) was 99.9%, the weight average molecular weight (Mw) was100,000, the molecular weight distribution (Mw/Mn) was 2.9, theisomerization ratio was 8%, and the melting point was 136° C.

(Preparation of Resin Composition)

0.1 part by weight oftetrakis[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane(Irganox 1010 manufactured by Ciba Geigy, hereinafter referred to as“Antioxidant A”) was added to 100 parts by weight of a hydrogenatedring-open polymer (11) and the mixture was kneaded using a twin-screwkneader (TEM35 manufactured by Toshiba Machine Co., Ltd.) to obtain apelletized resin composition.

(Preparation of Resin Sheet)

The pellets were pressed by a vacuum heat-press apparatus (manufacturedby Imoto Factory Co., Ltd.) at a die temperature of 150° C. under apressure of 8 MPa for five minutes, using a mold die with a thickness of1 mm, a length of 200 mm, and a width of 100 mm, with one side beingmirror plane processed, and cooled to room temperature at a cooling rateof 0.5° C./min to obtain a resin sheet (11) with a thickness of 300 μm.

Example 7 Ring-Opening Copolymerization

Polymerization was carried out in the same manner as in Example 6,except that the amount of the monomers used was 240 parts by weight of2-norbornene and 10 parts by weight of methyl norbornene, and the amountof 1-hexene was 0.55 parts by weight. The polymerization conversion ratewas about 100%. The weight average molecular weight (Mw) of theresulting ring-open polymer (10) was 81,500, and the molecular weightdistribution (Mw/Mn) was 1.8.

(Hydrogenation Reaction)

The polymerization reaction solution obtained above was transferred to apressure resistant hydrogenation reactor. After the addition of 0.5parts by weight of a nickel catalyst supported by diatomaceous earth(T8400, nickel support rate: 58 wt %, manufactured byNissan-Süd-Chemie), the hydrogenation reaction was carried out at 160°C. under a hydrogen pressure of 4.5 MPa for six hours. The reactionsolution was filtered through a stainless steel wire mesh filter, inwhich diatomaceous earth was used as a filtration adjuvant, to removethe catalyst. The filtrate was poured into 3000 parts by weight ofisopropyl alcohol while stirring to precipitate the hydrogenatedproduct. After washing with 500 parts by weight of acetone, thehydrogenated product was dried in a vacuum dryer at 100° C. under0.13×10³ Pa for 48 hours to obtain 190 parts by weight of a hydrogenatedring-open polymer (12).

(Properties of Polymer)

The degree of hydrogenation of the resulting hydrogenated ring-openpolymer (12) was 99.9%, the weight average molecular weight (Mw) was80,000, the molecular weight distribution (Mw/Mn) was 2.9, theisomerization ratio was 8%, and the melting point was 133° C.

(Preparation of Resin Composition)

0.1 part by weight of Antioxidant A was added to 100 parts by weight ofthe hydrogenated ring-open polymer (12) and the mixture was kneadedusing a twin-screw kneader (TEM35 manufactured by Toshiba Machine Co.,Ltd.) to obtain a pelletized resin composition.

(Preparation of Resin Sheet)

The pellets were pressed by a vacuum heat-press apparatus (manufacturedby Imoto Factory Co., Ltd.) at a die temperature of 150° C. under apressure of 8 MPa for five minutes, using a mold die with a thickness of1 mm, a length of 200 mm, and a width of 100 mm, with one side beingmirror plane processed, and cooled to room temperature at a cooling rateof 0.5° C./min to obtain a resin sheet (12) with a thickness of 300 μm.

Example 8 Ring-Opening Copolymerization

An autoclave equipped with a stirrer was charged with 37.1 parts byweight of a 70 wt % 2-norbornene solution in toluene, 0.26 parts byweight of dicyclopentadiene, 0.020 parts by weight of 1-hexene, and 49.3parts by weight of cyclohexane, and the mixture was stirred. Then, asolution containing 0.023 parts by weight ofbis(tricyclohexylphosphine)benzylidyneruthenium (IV) dichloride in 8.6parts by weight of toluene was added, and the reaction was carried outat 60° C. for 30 minutes. The polymerization conversion rate was about100%.

The weight average molecular weight (Mw) of the resulting ring-openpolymer (11) was 165,000, and the molecular weight distribution (Mw/Mn)was 1.3.

(Hydrogenation Reaction)

0.020 parts by weight of ethyl vinyl ether was added to the polymersolution obtained above and the mixture was stirred, followed by ahydrogenation reaction under a hydrogen pressure of 1.0 MPa at 150° C.for 20 hours. After cooling to room temperature, a suspension of 0.5parts by weight of the activated carbon in 10 parts by weight ofcyclohexane was added and the mixture was reacted under a hydrogenpressure of 1.0 MPa at 150° C. for two hours. The reaction mixture wasfiltered through a filter with a pore diameter of 0.2 μm to remove theactivated carbon. The reaction solution was poured into a large amountof isopropanol to cause the polymer to completely precipitate. Theprecipitate was collected by filtration. After washing with acetone, thehydrogenated product was dried in a vacuum dryer at 100° C. under0.13×10³ Pa for 48 hours to obtain a hydrogenated ring-open polymer(13).

(Properties of Polymer)

The degree of hydrogenation of the resulting hydrogenated ring-openpolymer (13) was 99.9%, the weight average molecular weight (Mw) was160,000, the molecular weight distribution (Mw/Mn) was 1.8, theisomerization ratio was 0%, and the melting point was 139° C.

(Preparation of Resin Composition)

0.1 part by weight of Antioxidant A was added to 100 parts by weight ofthe hydrogenated ring-open polymer (13) and the mixture was kneadedusing a twin-screw kneader to obtain a pelletized resin composition.

(Preparation of Resin Sheet)

The pellets were pressed by a vacuum heat-press apparatus (manufacturedby Imoto Factory Co., Ltd.) at a die temperature of 150° C. under apressure of 8 MPa for five minutes, using a mold die with a thickness of1 mm, a length of 200 mm, and a width of 100 mm, with one side beingmirror plane processed, and cooled to room temperature at a cooling rateof 0.5° C./min to obtain a resin sheet (13) with a thickness of 300 μm.

Example 9 Ring-Opening Copolymerization and Hydrogenation Reaction

A polymerization reaction was carried out in the same manner as inExample 6 except that the amount of the monomers used was 227.5 parts byweight of 2-norbornene and 22.5 parts by weight of methylnorbornene, andthe amount of other components was 0.4 parts by weight of 1-hexene, 0.40parts by weight of diisopropyl ether, 0.27 parts by weight oftriisobutylaluminum, 0.10 part by weight of isobutyl alcohol, and 20parts by weight of a 1.0 wt % tungsten hexachloride solution in toluene.The polymerization conversion rate was about 100%.

The weight average molecular weight (Mw) of the resulting ring-openpolymer (12) was 101,000, and the molecular weight distribution (Mw/Mn)was 2.8.

The hydrogenation reaction was carried out in the same manner as inExample 6 to obtain a hydrogenated norbornene ring-open polymer (14).

(Properties of Polymer)

The degree of hydrogenation of the resulting ring-open polymer (14) was99.9%, the weight average molecular weight (Mw) was 98,800, themolecular weight distribution (Mw/Mn) was 3.8, the isomerization ratiowas 7%, and the melting point was 114° C.

(Preparation of Resin Composition)

0.1 part by weight of Antioxidant A was added to 100 parts by weight ofthe hydrogenated ring-open polymer (14) and the mixture was kneadedusing a twin-screw kneader (TEM35 manufactured by Toshiba Machine Co.,Ltd.) to obtain a pelletized resin composition.

(Preparation of Resin Sheet)

The pellets were pressed by a vacuum heat-press apparatus (manufacturedby Imoto Factory Co., Ltd.) at a die temperature of 145° C. under apressure of 8 MPa for five minutes, using a mold die with a thickness of1 mm, a length of 200 mm, and a width of 100 mm, with one side beingmirror plane processed, and cooled to room temperature at a cooling rateof 0.5° C./min to obtain a resin sheet (14) with a thickness of 300 μm.

Example 10 Ring-Opening Copolymerization and Hydrogenation Reaction

A polymerization reaction was carried out in the same manner as inExample 6 except that the amount of the monomers used was 240 parts byweight of 2-norbornene and 10 parts by weight of dicyclopentadiene, andthe amount of other components was 0.55 parts by weight of 1-hexene,0.40 parts by weight of diisopropyl ether, 0.27 parts by weight oftriisobutylaluminum, 0.10 part by weight of isobutyl alcohol, and 20parts by weight of a 1.0 wt % tungsten hexachloride solution in toluene.The polymerization conversion rate was about 100%.

The weight average molecular weight (Mw) of the resulting ring-openpolymer (13) was 83,000, and the molecular weight distribution (Mw/Mn)was 2.7.

The hydrogenation reaction was carried out in the same manner as inExample 6 to obtain 190 parts by weight of a hydrogenated norbornenering-open polymer (15).

(Properties of Polymer)

The degree of hydrogenation of the resulting ring-open polymer (15) was99.9%, the weight average molecular weight (Mw) was 81,300, themolecular weight distribution (Mw/Mn) was 3.8, the isomerization ratiowas 9%, and the melting point was 134° C.

(Preparation of Resin Composition)

0.1 part by weight of Antioxidant A was added to 100 parts by weight ofthe hydrogenated ring-open polymer (15) and the mixture was kneadedusing a twin-screw kneader (TEM35 manufactured by Toshiba Machine Co.,Ltd.) to obtain a pelletized resin composition.

(Preparation of Resin Sheet)

The pellets were pressed by a vacuum heat-press apparatus (manufacturedby Imoto Factory Co., Ltd.) at a die temperature of 145° C. under apressure of 8 MPa for five minutes, using a mold die with a thickness of1 mm, a length of 200 mm, and a width of 100 mm, with one side beingmirror plane processed, and cooled to room temperature at a cooling rateof 0.5° C./min to obtain a resin sheet (15) with a thickness of 300 μm.

Example 11

A polymerization reaction was carried out in the same manner as inExample 6 except that the amount of the monomers used was 240 parts byweight of 2-norbornene and 10 parts by weight of dicyclopentadiene, andthe amount of other components was 0.15 parts by weight of 1-hexene,0.40 parts by weight of diisopropyl ether, 0.27 parts by weight oftriisobutylaluminum, 0.10 part by weight of isobutyl alcohol, and 20parts by weight of a 1.0 wt % tungsten hexachloride solution in toluene.The polymerization conversion rate was about 100%.

The weight average molecular weight (Mw) of the resulting ring-openpolymer (14) was 140,000, and the molecular weight distribution (Mw/Mn)was 7.1.

The hydrogenation reaction was carried out in the same manner as inExample 6 to obtain 190 parts by weight of a hydrogenated norbornenering-open polymer (16).

(Properties of Polymer)

The degree of hydrogenation of the resulting hydrogenated ring-openpolymer (16) was 99.9%, the weight average molecular weight (Mw) was137,000, the molecular weight distribution (Mw/Mn) was 7.8, theisomerization ratio was 9%, and the melting point was 134° C.

(Preparation of Resin Composition)

0.1 part by weight of Antioxidant A was added to 100 parts by weight ofthe hydrogenated ring-open polymer (16) and the mixture was kneadedusing a twin-screw kneader (TEM35 manufactured by Toshiba Machine Co.,Ltd.) to obtain a pelletized resin composition.

(Preparation of Resin Sheet)

The pellets were pressed by a vacuum heat-press apparatus (manufacturedby Imoto Factory Co., Ltd.) at a die temperature of 145° C. under apressure of 8 MPa for five minutes, using a mold die with a thickness of1 mm, a length of 200 mm, and a width of 100 mm, with one side beingmirror plane processed, and cooled to room temperature at a cooling rateof 0.5° C./min to obtain a resin sheet (16) with a thickness of 300 μm.

Comparative Example 5 Ring-Opening Copolymerization and HydrogenationReaction

Polymerization was carried out in the same manner as in Example 8,except that 200 parts by weight of methyltetracyclododecene (MTD) and 50parts by weight of dicyclopentadiene (DCP) were used instead of2-norbornene, and the amount of 1-hexene used was 0.40 parts by weight.The polymerization conversion rate was about 100%.

The weight average molecular weight (Mw) of the resulting ring-openpolymer (15) was 56,000, and the molecular weight distribution (Mw/Mn)was 3.7.

The hydrogenation reaction was carried out in the same manner as inExample 6, except that the amount of the nickel catalyst supported bydiatomaceous earth was 3 parts by weight, to obtain a hydrogenatednorbornene ring-open polymer (17).

(Properties of Polymer)

The degree of hydrogenation of the resulting hydrogenated ring-openpolymer (17) was 99.9%, the weight average molecular weight (Mw) was55,000, the molecular weight distribution (Mw/Mn) was 2.9, the glasstransition temperature was 140° C., and a melting point was notobserved.

(Preparation of Resin Composition)

0.1 part by weight of Antioxidant A was added to 100 parts by weight ofthe hydrogenated ring-open polymer (17) and the mixture was kneadedusing a twin-screw kneader (TEM35 manufactured by Toshiba Machine Co.,Ltd.) to obtain pellets.

(Preparation of Resin Sheet)

The pellets were pressed by a vacuum heat-press apparatus (manufacturedby Imoto Factory Co., Ltd.) at a die temperature of 220° C. under apressure of 8 MPa for five minutes, using a mold die with a thickness of1 mm, a length of 200 mm, and a width of 100 mm, with one side beingmirror plane processed, and cooled to room temperature at a cooling rateof 0.5° C./min to obtain a resin sheet (17) with a thickness of 300 μm.

Comparative Example 6 Ring-Opening Copolymerization and HydrogenationReaction

A polymerization reaction was carried out in the same manner as inExample 6 except for using 222.5 parts by weight of 2-norbornene and27.5 parts by weight of tetracyclododecene as monomers, and 0.07 partsby weight of 1-hexene, 0.4 parts by weight of diisopropyl ether, 0.27parts by weight of triisobutylaluminum, 0.10 part by weight of isobutylalcohol, and 20 parts by weight of a 1.0 wt % tungsten hexachloridesolution in toluene. The polymerization conversion rate was about 100%.

The weight average molecular weight (Mw) of the resulting ring-openpolymer (16) was 319,500, and the molecular weight distribution (Mw/Mn)was 3.4.

The hydrogenation reaction was carried out in the same manner as inExample 6, except that the amount of the nickel catalyst supported bydiatomaceous earth was 3 parts by weight, to obtain a hydrogenatednorbornene ring-open polymer (18).

(Properties of Polymer)

The degree of hydrogenation of the resulting hydrogenated ring-openpolymer (18) was 99.0%, the weight average molecular weight (Mw) was315,000, the molecular weight distribution (Mw/Mn) was 4.9, theisomerization ratio was 9%, and the melting point was 100° C.

(Preparation of Resin Composition)

0.1 part by weight of Antioxidant A was added to 100 parts by weight ofthe hydrogenated ring-open polymer (18) and the mixture was kneadedusing a twin-screw kneader (TEM35 manufactured by Toshiba Machine Co.,Ltd.) to obtain a pelletized resin composition.

(Preparation of Resin Sheet)

The pellets were pressed by a vacuum heat-press apparatus (manufacturedby Imoto Factory Co., Ltd.) at a die temperature of 135° C. under apressure of 8 MPa for five minutes, using a mold die with a thickness of1 mm, a length of 200 mm, and a width of 100 mm, with one side beingmirror plane processed, and cooled to room temperature at a cooling rateof 0.5° C./min to obtain a resin sheet (18) with a thickness of 300 μm.

Reference Example 2

0.1 part by weight of Antioxidant A was added to 100 parts by weight ofthe hydrogenated ring-open polymer (8) obtained in Reference Example 1and the mixture was kneaded using a twin-screw kneader (TEM35manufactured by Toshiba Machine Co., Ltd.) to obtain a pelletized resincomposition.

(Preparation of Resin Sheet)

The pellets were pressed by a vacuum heat-press apparatus (manufacturedby Imoto Factory Co., Ltd.) at a die temperature of 150° C. under apressure of 8 MPa for five minutes, using a mold die with a thickness of1 mm, a length of 200 mm, and a width of 100 mm, with one side beingmirror plane processed, and cooled to room temperature at a cooling rateof 0.5° C./min to obtain a resin sheet (19) with a thickness of 300 μm.

Comparative Example 7

0.1 part by weight of Antioxidant A was added to 100 parts by weight ofthe hydrogenated ring-open polymer (7) obtained in Comparative Example 2and the mixture was kneaded using a twin-screw kneader (TEM35manufactured by Toshiba Machine Co., Ltd.) to obtain a pelletized resincomposition.

(Preparation of Resin Sheet)

The pellets were pressed by a vacuum heat-press apparatus (manufacturedby Imoto Factory Co., Ltd.) at a die temperature of 280° C. under apressure of 8 MPa for five minutes, using a mold die with a thickness of1 mm, a length of 200 mm, and a width of 100 mm, with one side beingmirror plane processed, and cooled to room temperature at a cooling rateof 0.5° C./min to obtain a resin sheet (20).

(Solubility Evaluation Test (c-Hex Solubility))

Solubility in cyclohexane was evaluated using the hydrogenated ring-openpolymers (11) to (18), (8), and (7). The solubility was judged bypreparing a cyclohexane solution of the ring-open polymer with aconcentration of 20% at 70° C. and cooling the solution, while observingthe temperature at which the polymer was deposited with the naked eye.The results are shown in Table 3.

(Processability Evaluation Test (1))

Processability was evaluated using the hydrogenated ring-open polymers(11) to (18), (8), and (7). The processability was evaluated bymeasuring the thickness of monolayer films (C1) (thickness: 100 μm)obtained by molding the pellets of the hydrogenated ring-open polymer(11) to (18), (8), and (7) by T-die molding using a hanger manifoldT-die film melt extruding press machine (stationary type manufactured byGSI Creos Corp.) equipped with a screw having a screw diameter of 20 mm,a compression ratio of 2.5 or 3.1, and L/D=30 under the followingconditions. The results are shown in Table 4.

Specifically, the film thickness was measured at 100 points in the MDdirection at intervals of 2.5 m using a micro gage to calculate thestandard deviation (σ).

<Molding Conditions> Die lip: 0.8 mm

Molten resin temperature: Tm of resin+40° C. (resin without a meltingpoint: Tg+100° C.)

Width of T-die: 300 mm

T-die temperature: Tm of resin+50° C. (resin without a melting point:Tg+110° C.)Cooling roll: Tm of resin−20° C. (resin without a melting point: Tg−15°C.)Casting roll: Tm of resin−10° C. (resin without a melting point: Tg−5°C.)Sheet roll-up rate: 2.5 m/minScrew compression ratio: a screw with a compression ratio of 2.5 wasused for resins having no melting point, and a screw with a compressionratio of 3.1 was used for other resins.

(Processability Evaluation Test (2))

The processability were evaluated by the film thickness variation whenmonolayer films (C1) (thickness: 100 μm) were continuously produced foreight hours and the time before a die line was generated (die linegeneration time) using the same extruding press machine as used in theprocessability evaluation test (1), of which the conditions were set sothat the resin pressure at the die portion is 3 MPa on average.

The same process conditions as in the processability evaluation test (1)were employed, except that the molten resin temperature and the T-dietemperature shown in the following Table 3 were used when processing thehydrogenated ring-open polymers (11) to (18), (8), and (7).

TABLE 3 Hydrogenated ring- Molten resin temperature T-die temperatureopen (co)polymer (° C.) (° C.) 11 170 180 12 170 180 13 190 200 14 155165 15 175 185 16 190 200 17 240 250 18 235 245 8 175 185 7 315 325

Specifically, at every one hour after the start of film formation, thefilm thickness was measured at 10 points in the MD direction atintervals of 2.5 m (total of 80 points) using a micro gage to calculatethe standard deviation. The time required for the die line to begenerated from the start of film formation was measured by visuallyjudging the occurrence of the die line.

The term “die line” refers to a streak, observable with the naked eye,continuously generated along the direction of extrusion of the resin atthe position of the molded article corresponding to the specificposition of the die. Specifically, the die line is a streak formed onthe surface of the molded article consisting of irregularities (concavesand convexes) with a height of about 0.3 μm to 100 μm. Smaller concavesand convexes cannot be observed with the naked eye.

(Measurement of Tensile Breaking Elongation)

Tensile breaking elongation was measured for each of the resin sheets(11) to (20) obtained in the above. Tensile breaking elongation wasmeasured according to ISO 527 at a tensile velocity of 200 mm/min usingan Autograph (AGS-5kNH, manufactured by Shimadzu Corp.). The measurementresults are shown in Table 4.

(Evaluation Test of Steam Barrier Properties)

Moisture permeability of each of the sheets (11) to (20) obtained abovewas evaluated. The moisture permeability was measured according to JISK7129 (method A) using a moisture permeability tester (L80-5000 type,manufactured by LYSSY) under conditions of a temperature of 40° C. andhumidity of 90% RH. The measurement results are shown in Table 4. Asmall moisture permeability (g/(m²·24 h)) indicates good steam barrierproperties.

(Evaluation of Oil Resistance)

Oil resistance of each of the sheets (11) to (20) obtained above wasevaluated. Critical stress to salad oil (manufactured by Nisshin OillioGroup, Ltd.) was used for evaluation of the oil resistance. Afterapplying salad oil to the surface of a test specimen with dimensions of10 mm×100 mm×1 mm prepared by heat-pressing, the test specimen wassecured for one hour to a curvature of an aluminum jig made by cuttingan elliptic cylinder with a height of 10 mm, a major ellipse axis of 200mm and a minor ellipse axis of 80 mm into four equal divisions, toobserve whether or not cracks were produced in the test specimen. Alltest specimens were secured at fixed positions. For a test specimen inwhich the cracks were generated, the crack generating positions weremeasured taking the end of the test specimen on the low curvature sideat the time of securing as the starting point. The results are shown inTable 4.

(Measurement of Haze)

Haze of each of the sheets (11) to (20) obtained above was measured.Samples with a thickness of 300 μm were prepared and the haze wasmeasured using a haze meter (NDH2000 manufactured by Nippon DenshokuCo., Ltd.). The measurement results are shown in Table 4.

TABLE 4 Processability Processability evaluation (2) c-Hex evaluation(1) Time Tensile Hydrogenated solubility Standard Standard before diebreaking Moisture ring-open (deposition Resin deviation deviation lineelongation permeability Haze Oil polymer temperature) sheet (σ) (σ)formation (%) (g/(m² · 24 h)) (%) resistance Example 6 11 62° C. 11 6 μm3 μm ≧15 hrs 33 0.23 30.1 No cracks 7 12 57° C. 12 8 μm 4 μm ≧15 hrs 350.24 28.0 No cracks 8 13 60° C. 13 6 μm 4 μm  10 hrs 35 0.24 27.2 Nocracks 9 14 49° C. 14 9 μm 4 μm ≧15 hrs 37 0.40 22.2 No cracks 10 15 62°C. 15 8 μm 4 μm ≧15 hrs 30 0.30 26.0 No cracks 11 16 58° C. 16 8 μm 4 μm≧15 hrs 35 0.30 29.0 No cracks Comparative 5 17 ≦25° C.  17 5 μm 4 μm≧15 hrs 40 0.98 0.9 Cracks at Example 45 mm 6 18 40° C. 18 15 μm  7 μm   3 hrs 25 0.78 21.4 No cracks Reference 2 8 69° C. 19 18 μm  10 μm  13 hrs 25 0.23 41.0 No cracks Example Comparative 7 7 did not 20 10 μm 8 μm    2 hrs 15 0.78 28.0 No cracks Example dissolve

As shown in Table 4, the hydrogenated ring-open polymers (11) to (16) ofExamples 6 to 11 and the hydrogenated ring-open polymers (18) and (8) ofComparative Example 6 and Reference Example 2 showed excellentsolubility. On the other hand, the hydrogenated ring-open polymer (7) ofComparative Example 7 showed poor solubility.

The hydrogenated ring-open polymers (11) to (16) of Examples 6 to 11 andthe hydrogenated ring-open polymer (17) of Comparative Example 5 showedexcellent processability as compared with the hydrogenated ring-openpolymers (18), (8), and (7) of Comparative Examples 6 and 7, andReference Example 2.

The resin sheets (11) to (16) of Examples 6 to 11 exhibited excellentmechanical properties as indicated by the tensile breaking elongation of30% or more. On the other hand, the resin sheets (18) to (20) ofComparative Examples 6, 7 and Reference Example 2 exhibited poormechanical properties as indicated by the tensile breaking elongation of25% or less.

The moisture permeability of the resin sheets (11) to (16) of Examples 6to 11 and the resin sheet (19) of Reference Example 2 was 0.40 g/(m²·24h) or less, indicating excellent steam barrier properties. The moisturepermeability of the resin sheets (17), (18), and (20) of ComparativeExamples 5, 6, and 7 was 0.78 g/(m²·24 h) or more, indicating poor steambarrier properties of these resin sheets.

The haze of the resin sheets (11) to (16) of Examples 6 to 11 and theresin sheets (17), (18), and (20) of Comparative Examples 5, 6, and 7was 30.1% or less. On the other hand, the haze of resin sheet (19) ofReference Example 2 was 41.0% indicating poor transparency.

The resin sheets (11) to (16) of Examples 6 to 11 and the resin sheets(18) to (20) of Comparative Examples 6 and 7, and Reference Example 2exhibited excellent oil resistance. On the other hand, the resin sheet(17) of Comparative Example 5 exhibited poor oil resistance.

Based on the above results, the hydrogenated ring-open polymers andresin sheets of Examples 6 to 11 can be regarded as excellent in allperformance, including steam barrier properties, heat resistance, oilresistance, mechanical properties, transparency, and processabilitydemanded in recent years in the fields of information processing, foodindustries, medical supplies, engineering works, and the like.

Example 12

0.1 part by weight of an antioxidant(tetrakis[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane(Irganox 1010 manufactured by Ciba Geigy)) was added to 100 parts byweight of the hydrogenated ring-open polymer (1) obtained in Example 1,and the mixture was kneaded using a twin-screw kneader (TEM35manufactured by Toshiba Machine Co., Ltd.) to obtain a pelletized resincomposition.

(Preparation of Tube Sheet)

The pellets were processed by an inflation machine (manufactured bySumitomo Heavy Industries Modern, Ltd.) to produce a tube sheet (A) witha thickness of 250 μm under the conditions of a lip clearance of 2.5 mm,a drawing speed of 8 m/min, and a die temperature of 190° C.

Example 13

0.1 part by weight of an antioxidant(tetrakis[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane(Irganox 1010 manufactured by Ciba Geigy)) was added to 100 parts byweight of the hydrogenated ring-open polymer (11) obtained in Example 6,and the mixture was kneaded using a twin-screw kneader (TEM35manufactured by Toshiba Machine Co., Ltd.) to obtain a pelletized resincomposition.

(Preparation of Tube Sheet)

The pellets and low density polyethylene (Novatech SF720: density 0.928g/cm³, manufactured by Japan Polyethylene Corp.) were processed by aninflation machine (manufactured by Sumitomo Heavy Industries Modern,Ltd.) to produce a tube sheet (B) with a thickness of 250 μm, consistingof a layer of the hydrogenated ring-open polymer (11) (thickness: 30 μm)and a layer of the low density polyethylene (thickness: 220 μm) underthe conditions of a lip clearance of 2.5 mm, a drawing speed of 8 m/min,and a die temperature of 190° C.

Example 14

0.1 part by weight of an antioxidant(tetrakis[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane(Irganox 1010 manufactured by Ciba Geigy)) was added to 100 parts byweight of the hydrogenated ring-open polymer (14) obtained in Example 9,and the mixture was kneaded using a twin-screw kneader (TEM35manufactured by Toshiba Machine Co., Ltd.) to obtain a pelletized resincomposition.

(Preparation of Tube Sheet)

The pellets and low density polyethylene (Novatech SF720: density 0.928g/cm³, manufactured by Japan Polyethylene Corp.) were processed by aninflation machine (manufactured by Sumitomo Heavy Industries Modern,Ltd.) to produce a tube sheet (C) with a thickness of 250 μm, consistingof a layer of the hydrogenated ring-open polymer (14) (thickness: 30 μm)and a layer of the low density polyethylene (thickness: 220 μm) underthe conditions of a lip clearance of 2.5 mm, a drawing speed of 8 m/min,and a die temperature of 190° C.

Example 15

0.1 part by weight of an antioxidant(tetrakis[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane(Irganox 1010 manufactured by Ciba Geigy)) was added to 100 parts byweight of the hydrogenated ring-open polymer (5) obtained in Example 5,and the mixture was kneaded using a twin-screw kneader (TEM35manufactured by Toshiba Machine Co., Ltd.) to obtain a pelletized resincomposition.

(Preparation of Tube Sheet)

The pellets and low density polyethylene (Novatech SF720: density 0.928g/cm³, manufactured by Japan Polyethylene Corp.) were processed by aninflation machine (manufactured by Sumitomo Heavy Industries Modern,Ltd.) to produce a tube sheet (D) with a thickness of 250 μm, consistingof a layer of the hydrogenated ring-open polymer (5) (thickness: 30 μm)and a layer of the low density polyethylene (thickness: 220 μm) underthe conditions of a lip clearance of 2.5 mm, a drawing speed of 8 m/min,and a die temperature of 190° C.

Example 16

0.1 part by weight of an antioxidant(tetrakis[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane(Irganox 1010 manufactured by Ciba Geigy)) was added to 100 parts byweight of the hydrogenated ring-open polymer (3) obtained in Example 3,and the mixture was kneaded using a twin-screw kneader (TEM35manufactured by Toshiba Machine Co., Ltd.) to obtain a pelletized resincomposition.

(Preparation of Tube Sheet)

The pellets and low density polyethylene (Novatech SF720: density 0.928g/cm³, manufactured by Japan Polyethylene Corp.) were processed by aninflation machine (manufactured by Sumitomo Heavy Industries Modern,Ltd.) to produce a tube sheet (E) with a thickness of 250 μm, consistingof a layer of the hydrogenated ring-open polymer (3) (thickness: 30 μm)and a layer of the low density polyethylene (thickness: 220 μm) underthe conditions of a lip clearance of 2.5 mm, a drawing speed of 8 m/min,and a die temperature of 190° C.

Example 17

0.1 part by weight of an antioxidant(tetrakis[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane(Irganox 1010 manufactured by Ciba Geigy)) was added to 100 parts byweight of the hydrogenated ring-open polymer (15) obtained in Example10, and the mixture was kneaded using a twin-screw kneader (TEM35manufactured by Toshiba Machine Co., Ltd.) to obtain a pelletized resincomposition.

(Preparation of Tube Sheet)

The pellets of the hydrogenated ring-open polymer (15) were processed byan inflation machine (manufactured by Sumitomo Heavy Industries Modern,Ltd.) to produce a tube sheet (F) with a thickness of 250 μm under theconditions of a lip clearance of 2.5 mm, a drawing speed of 8 m/min, anda die temperature of 190° C.

Example 18 Preparation of Tube Sheet

The pellets of the hydrogenated ring-open polymer (15) and low densitypolyethylene (Novatech SF720: density 0.928 g/cm³, manufactured by JapanPolyethylene Corp.) were processed by an inflation machine (manufacturedby Sumitomo Heavy Industries Modern, Ltd.) to produce a tube sheet (G)with a thickness of 250 μm, consisting of a layer of the hydrogenatedring-open polymer (15) (thickness: 30 μm) and a layer of the low densitypolyethylene (thickness: 220 μm) under the conditions of a lip clearanceof 2.5 mm, a drawing speed of 8 m/min, and a die temperature of 190° C.

Example 19 Preparation of Tube Sheet

The pellets of the hydrogenated ring-open polymer (1) and low densitypolyethylene (Novatech SF720: density 0.928 g/cm³, manufactured by JapanPolyethylene Corp.) were processed by an inflation machine (manufacturedby Sumitomo Heavy Industries Modern, Ltd.) to produce a tube sheet (H)with a thickness of 250 μm, consisting of three layers of a low densitypolyethylene layer (thickness: 110 μm), a hydrogenated ring-open polymer(1) layer (thickness: 30 μm), and a low density polyethylene layer(thickness: 110 μm) under the conditions of a lip clearance of 2.5 mm, adrawing speed of 8 m/min, and a die temperature of 190° C.

Example 20

0.1 part by weight of an antioxidant(tetrakis[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane(Irganox 1010 manufactured by Ciba Geigy)) was added to 100 parts byweight of the hydrogenated ring-open polymer (8) obtained in ReferenceExample 1, and the mixture was kneaded using a twin-screw kneader (TEM35manufactured by Toshiba Machine Co., Ltd.) to obtain pellets.

(Preparation of Tube Sheet)

The pellets of the hydrogenated ring-open polymer (8) and low densitypolyethylene (Novatech SF720: density 0.928 g/cm³, manufactured by JapanPolyethylene Corp.) were processed by an inflation machine (manufacturedby Sumitomo Heavy Industries Modern, Ltd.) to produce a tube sheet (I)with a thickness of 250 μm, consisting of a layer of the hydrogenatedring-open polymer (8) (thickness: 30 μm) and a layer of the low densitypolyethylene (thickness: 220 μm) under the conditions of a lip clearanceof 2.5 mm, a drawing speed of 8 m/min, and a die temperature of 190° C.

Comparative Example 8

0.1 part by weight of an antioxidant(tetrakis[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane(Irganox 1010 manufactured by Ciba Geigy)) was added to 100 parts byweight of the hydrogenated ring-open polymer (18) obtained inComparative Example 6, and the mixture was kneaded using a twin-screwkneader (TEM35 manufactured by Toshiba Machine Co., Ltd.) to obtain apelletized resin composition.

(Preparation of Tube Sheet)

The pellets of the hydrogenated ring-open polymer (17) and low densitypolyethylene (Novatech SF720: density 0.928 g/cm³, manufactured by JapanPolyethylene Corp.) were processed by an inflation machine (manufacturedby Sumitomo Heavy Industries Modern, Ltd.) to produce a tube sheet (J)with a thickness of 250 μm, consisting of a layer of the hydrogenatedring-open polymer (17) (thickness: 30 μm) and a layer of the low densitypolyethylene (thickness: 220 μm) under the conditions of a lip clearanceof 2.5 mm, a drawing speed of 8 m/min, and a die temperature of 190° C.

Comparative Example 9

0.1 part by weight of an antioxidant(tetrakis[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane(Irganox 1010 manufactured by Ciba Geigy)) was added to 100 parts byweight of the hydrogenated ring-open polymer (17) obtained inComparative Example 5, and the mixture was kneaded using a twin-screwkneader (TEM35 manufactured by Toshiba Machine Co., Ltd.) to obtain apelletized resin composition.

(Preparation of Tube Sheet)

The pellets of the hydrogenated ring-open polymer (17) and low densitypolyethylene (Novatech SF720: density 0.928 g/cm³, manufactured by JapanPolyethylene Corp.) were processed by an inflation machine (manufacturedby Sumitomo Heavy Industries Modern, Ltd.) to produce a tube sheet (K)with a thickness of 250 μm, consisting of a layer of the hydrogenatedring-open polymer (16) (thickness: 30 μm) and a layer of the low densitypolyethylene (thickness: 220 μm) under the conditions of a lip clearanceof 2.5 mm, a drawing speed of 8 m/min, and a die temperature of 260° C.

Comparative Example 10

0.1 part by weight of an antioxidant(tetrakis[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane(Irganox 1010 manufactured by Ciba Geigy)) was added to 100 parts byweight of the hydrogenated ring-open polymer (7) obtained in ComparativeExample 2, and the mixture was kneaded using a twin-screw kneader (TEM35manufactured by Toshiba Machine Co., Ltd.) to obtain pellets.

(Preparation of Tube Sheet)

The pellets and low density polyethylene (Novatech SF720: density 0.928g/cm³, manufactured by Japan Polyethylene Corp.) were processed by aninflation machine (manufactured by Sumitomo Heavy Industries Modern,Ltd.) to produce a tube sheet (L) with a thickness of 250 μm, consistingof a layer of the hydrogenated ring-open polymer (7) (thickness: 30 μm)and a layer of the low density polyethylene (thickness: 220 μm) underthe conditions of a lip clearance of 2.5 mm, a drawing speed of 8 m/min,and a die temperature of 285° C.

Comparative Example 11 Preparation of Tube Sheet

A low density polyethylene (Novatech SF720: density 0.928 g/cm³,manufactured by Japan Polyethylene Corp.) was processed by an inflationmachine (manufactured by Sumitomo Heavy Industries Modern, Ltd.) toproduce a tube sheet (M) made of the low density polyethylene with athickness of 250 μm under the conditions of a lip clearance of 2.5 mm, adrawing speed of 8 m/min, and a die temperature of 190° C.

The number of hydrogenated ring-open polymers of Examples 12 to 20 andComparative Examples 8 to 11, the composition, Mw, Mw/Mn, hydrogenationdegree (%), isomerization ratio (%), melting point, and the tube sheetconstitution are shown in Table 5.

TABLE 5 Hydrogenated ring-open polymer Melting Tube HydrogenationIsomerization point Layer sheet No. Composition Mw Mw/Mn rate (%) rate(%) (° C.) constitution Example 12 A 1 NB 100 82200 2.9 99.9 5 140 A 13B 11 NB/MNB = 98/2 100000 2.9 99.9 8 136 PE/B 14 C 14 NB/MNB = 91/998800 3.8 99.9 7 114 PE/C 15 D 5 NB 100 185000 4.4 99.9 10 136 PE/D 16 E3 NB 100 81600 2.8 99.9 35 125 PE/E 17 F 15 NB/DCP = 96/4 81300 3.8 99.99 134 F 18 G 15 NB/DCP = 96/4 81300 3.8 99.9 9 134 PE/F 19 H 1 NB 10082200 2.9 99.9 5 140 PE/A/PE 20 I 8 NB 100 64200 1.3 99.75 0 143 PE/GComparative 8 J 18 NB/TCD = 89/11 315000 4.9 99.0 9 100 PE/H Example 9 K17 MTD/DCP = 80/20 55000 2.9 99.9 — — PE/I 10 L 7 DCP 100 — — — — 273PE/J 11 M — — — — — — — PE PE = Polyethylene

The thickness fluctuation, moisture permeability at 40° C., moisturepermeability at 50° C., modulus of elasticity, strain at the time ofcrack generation, and haze change when salad oil was applied weremeasured and evaluated using the tube sheets (A) to (M). In themeasurement and evaluation of the thickness fluctuation, moisturepermeability at 40° C., moisture permeability at 50° C., and haze changewhen salad oil was applied, a sheet with a thickness of 250 μm producedby cutting the side of the tube sheet was used. The modulus ofelasticity and strain at the time of crack generation were evaluatedusing a dumbbell form test specimen 1B type with a thickness of 250 μmbased on ISO527. The results are shown in Table 6.

TABLE 6 Strain at the Haze change Thickness Modulus of time of crackbefore and after Tube Layer Thickness standard Steam barrier propertieselasticity generation salad oil sheet constitution (μm) deviation 40° C.× 90% RH 50° C. × 90% RH (MPa) (%) application* Example 12 A A 250 6.20.09 0.23 420 27 0.86 13 B PE/B 220/30 6.5 0.42 1.48 362 30 0.94 14 CPE/C 220/30 6.9 0.52 1.78 360 37 0.94 15 D PE/D 220/30 7.4 0.47 1.68 35825 0.97 16 E PE/E 220/30 6.5 0.44 1.50 360 34 0.94 17 F F 250 6.4 0.180.68 390 32 0.86 18 G PE/F 220/30 7.0 0.52 1.72 342 32 0.94 19 H PE/A/PE110/30/110 6.4 0.43 1.49 358 28 1.00 20 I PE/G 220/30 7.9 0.46 1.58 38624 0.86 Comparative 8 J PE/H 220/30 7.8 0.68 2.48 380 28 0.98 Example 9K PE/J 220/30 13.4 0.87 3.65 680 28 0.44 10 L PE/K 220/30 18.4 0.76 2.86720 17 0.90 11 M PE 250 6.4 1.00 6.40 350 ≧50 1.00 *Haze withouttreating with salad oil/haze after salad oil attachment

As shown in Table 6, the tube sheets (A) to (I), (J), and (M) ofExamples 12 to 20 and Comparative Examples 8 and 11 had small thicknessstandard deviation values, indicating a small thickness fluctuation. Onthe other hand, the tube sheets (K) and (L) of Comparative Examples 9and 10 had comparatively large thickness standard deviation values,indicating their comparatively large thickness fluctuation.

The tube sheets (A) to (I) of Examples 12 to 20 showed excellent steambarrier properties particularly at a high temperature (50° C.). The tubesheets (J) to (M) of Comparative Examples 8 to 11 showed poor steambarrier properties particularly at a high temperature (50° C.).

The tube sheets (A) to (I) of Examples 12 to 20 and the tube sheets (J)and (M) of Comparative Examples 8 and 11 had a modulus of elasticity of420 MPa or less, indicating their excellent pliability. On the otherhand, the tube sheets (K) and (L) of Comparative Examples 9 and 10 hadmodulus of elasticity of 680 MPa or more, indicating their poorpliability.

The tube sheets (B), (C), and (E) to (G) of Examples 13, 14, and 16 to18 exhibited particularly excellent mechanical properties as indicatedby the strain at the time of crack generation of 30% or more. In thesame manner as the tube sheets of Comparative Examples 8, 9 and 11, thetube sheets (A) to (I) of Examples 12 to 20 had excellent mechanicalproperties as indicated by the strain at the time of crack generation of24% or more, indicating their excellent mechanical properties. On theother hand, the tube sheet (L) of Comparative Example 10 had a strain atthe time of crack generation of 17%, indicating its poor mechanicalproperties.

In the same manner as the tube sheets of (J), (L), and (M) ofComparative Examples 8, 10 and 11, the tube sheets (A) to (I) ofExamples 12 to 20 had excellent oil resistance as indicated by thechange in the haze value due to the application of salad oil. On theother hand, the tube sheet (K) of Comparative Example 9 showed asignificant change of the haze value due to salad oil application,indicating its poor oil resistance.

Since the tube sheets of Examples 12 to 20 have excellent steam barrierproperties, mechanical characteristics, oil resistance, pliability, andmoldability, and particularly superior steam barrier properties at ahigh temperature, the tube sheets are preferable as a packing materialof an infusion solution bag.

Pellet Production Example 1

0.1 part by weight of an antioxidant(tetrakis[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane(Irganox 1010 manufactured by Ciba Geigy), hereinafter referred to as“Antioxidant A”) was added to 100 parts by weight of the hydrogenatedring-open polymer (1) and the mixture was kneaded using a twin-screwkneader (TEM35B manufactured by Toshiba Machine Co., Ltd.) to obtainpellets (A).

Pellet Production Example 2

0.1 part by weight of Antioxidant A was added to 100 parts by weight ofthe hydrogenated ring-open polymer (11) obtained in Example 6 and themixture was kneaded using a twin-screw kneader (TEM35B manufactured byToshiba Machine Co., Ltd.) to obtain pellets (B).

Pellet Production Example 3

0.1 part by weight of Antioxidant A was added to 100 parts by weight ofthe hydrogenated ring-open polymer (12) obtained in Example 7 and themixture was kneaded using a twin-screw kneader (TEM35B manufactured byToshiba Machine Co., Ltd.) to obtain pellets (C).

Pellet Production Example 4

0.1 part by weight of Antioxidant A was added to 100 parts by weight ofthe hydrogenated ring-open polymer (14) obtained in Example 9 and themixture was kneaded using a twin-screw kneader (TEM35B manufactured byToshiba Machine Co., Ltd.) to obtain pellets (D).

Pellet Production Example 5

0.1 part by weight of Antioxidant A was added to 100 parts by weight ofthe hydrogenated ring-open polymer (13) obtained in Example 8 and themixture was kneaded using a twin-screw kneader to obtain pellets (E).

Pellet Production Example 6

0.1 part by weight of Antioxidant A was added to 100 parts by weight ofthe hydrogenated ring-open polymer (15) obtained in Example 10 and themixture was kneaded using a twin-screw kneader (TEM35B manufactured byToshiba Machine Co., Ltd.) to obtain pellets (F).

Pellet Production Example 7

0.1 part by weight of Antioxidant A was added to 100 parts by weight ofthe hydrogenated ring-open polymer (8) obtained in Reference Example 1and the mixture was kneaded using a twin-screw kneader (TEM35Bmanufactured by Toshiba Machine Co., Ltd.) to obtain pellets (G).

Pellet Production Example 8 Ring-Opening Polymerization andHydrogenation Reaction

Polymerization was carried out in the same manner as in PelletProduction Example 1, except that 200 parts by weight ofmethyltetracyclododecene (MTD) and 50 parts by weight ofdicyclopentadiene were used instead of 2-norbornene, and the amount of1-hexene used was 0.40 parts by weight. The polymerization conversionrate was about 100%. The weight average molecular weight (Mw) of theresulting ring-open polymer (17) was 56,000, and the molecular weightdistribution (Mw/Mn) was 2.0. The hydrogenation reaction was carried outin the same manner as in Pellet Production Example 3 to obtain ahydrogenated ring-open polymer (19).

(Properties of Polymer)

The degree of hydrogenation of the resulting hydrogenated ring-openpolymer (19) was 99.9%, the weight average molecular weight (Mw) was55,000, the molecular weight distribution (Mw/Mn) was 3.1, the glasstransition temperature was 140° C., and a melting point was notobserved.

(Preparation of Resin Composition)

0.1 part by weight of Antioxidant A was added to 100 parts by weight ofthe hydrogenated ring-open polymer (19) and the mixture was kneadedusing a twin-screw kneader (TEM35B manufactured by Toshiba Machine Co.,Ltd.) to obtain pellets (H).

Pellet Production Example 9 Ring-Opening Polymerization andHydrogenation Reaction

0.1 part by weight of Antioxidant A was added to 100 parts by weight ofthe hydrogenated ring-open polymer (18) obtained in Comparative Example6 and the mixture was kneaded using a twin-screw kneader (TEM35Bmanufactured by Toshiba Machine Co., Ltd.) to obtain pellets (I).

Pellet Production Example 10

0.1 part by weight of Antioxidant A was added to 100 parts by weight ofthe hydrogenated ring-open polymer (7) obtained in Comparative Example 2and the mixture was kneaded using a twin-screw kneader (TEM35Bmanufactured by Toshiba Machine Co., Ltd.) to obtain pellets (J).

Example 21 Sheet Forming

The pellets (A) were molded into a monolayer sheet (A) (thickness: 250μm) by T-die molding using a hanger manifold T-die film melt extrudingpress machine (stationary type manufactured by GSI Creos Corp.) equippedwith a screw having a screw diameter of 20 mm, a compression ratio of3.1, and L/D=30 under the following conditions.

The type, composition, Mw, Mw/Mn, hydrogenation degree (%),isomerization ratio (%), and melting point (° C.) of the hydrogenatedring-open polymer forming the monolayer sheet (A) are shown in Table 7.

<Molding Conditions> Die lip: 0.8 mm

Molten resin temperature: 180° C.

Width of T-die: 300 mm

Cooling roller: 120° C.Casting roll: 130° C.

The monolayer sheet (A) obtained above was molded by blister molding at130° C. using a medication packing machine (FBP-M2 manufactured by CKD)to obtain a process sheet (1) having 10 cylindrical portions (pockets:diameter 9 mm×height 5 mm) arranged five lengthwise and two horizontallyat center intervals of 15 mm, for enclosing tablets (8 mm φ×maximumthickness of 4 mm) on the monolayer film (A).

The oil resistance of the resulting process sheet (1) was evaluated. Theresults are shown in Table 8.

Without filling the medication, the plane on the concave side(unprojected side) of the pocket of the process sheet (1) was layeredwith the adhesive plane of an aluminum foil for PTP (manufactured byNippon Foil Mfg. Co., Ltd.) (thickness 20 μm). After heat-sealing at210° C. and inserting a slitter at 175° C., the layered material waspunched to obtain a PTP (1) with a width of 37 mm, a length of 94 mm,and a corner of 5 mmR, having a total of ten pockets (five lengthwiseand two horizontally). The blister moldability of the pockets of theresulting PTP (1) was evaluated. The results are shown in Table 8.

Table 8 also shows the steam barrier properties of the monolayer sheet(A).

Example 22 Sheet Forming

The pellets (B) were molded into a monolayer sheet (B) (thickness: 250μm) by T-die molding using a hanger manifold T-die film melt extrudingpress machine (stationary type manufactured by GSI Creos Corp.) equippedwith a screw having a screw diameter of 20 mm, a compression ratio of3.1, and L/D=30 under the following conditions.

The type, composition, Mw, Mw/Mn, hydrogenation degree (%),isomerization ratio (%), and melting point (° C.) of the hydrogenatedring-open polymer forming the monolayer sheet (B) are shown in Table 7.

<Molding Conditions> Die lip: 0.8 mm

Molten resin temperature: 180° C.

Width of T-die: 300 mm

Cooling roller: 120° C.Casting roll: 130° C.

A process sheet (2) and a PTP (2) were prepared in the same manner as inExample 21, except for using the monolayer sheet (B) instead of themonolayer sheet (A). Steam barrier properties of the monolayer sheet(B), oil resistance of the resulting process sheet (2), and the blistermoldability of the pockets of the PTP (2) were evaluated. Themeasurement results are shown in Table 8.

Table 8 also shows the steam barrier properties of the monolayer sheet(B).

Example 23 Sheet Forming

The pellets (C) were molded into a monolayer sheet (C1) (thickness: 250μm), a monolayer sheet (C2) (thickness: 215 μm), and a monolayer sheet(C3) (thickness: 180 μm) by T-die molding using a hanger manifold T-diefilm melt extruding press machine (stationary type manufactured by GSICreos Corp.) equipped with a screw having a screw diameter of 20 mm, acompression ratio of 3.1, and L/D=30 under the following conditions.

The type, composition, Mw, Mw/Mn, hydrogenation degree (%),isomerization ratio (%), and melting point (° C.) of the hydrogenatedring-open polymer forming the monolayer sheet (C1) are shown in Table 7.

<Molding Conditions> Die lip: 0.8 mm

Molten resin temperature: 180° C.

Width of T-die: 300 mm

Cooling roller: 120° C.Casting roll: 130° C.

A process sheet (3) was prepared in the same manner as in Example 21,except that the monolayer sheet (C1) was used instead of the monolayersheet (A) and the blister molding temperature was 120° C. The resultingprocess sheet (3) was molded in the same manner as in Example 21 toobtain a PTP (3). Oil resistance of the resulting PTP (3) and blistermoldability of the pockets of the PTP (3) were evaluated. The resultsare shown in Table 8.

Table 8 also shows the steam barrier properties of the monolayer sheet(C1).

Example 24 Sheet Forming

The pellets (D) were molded into a monolayer sheet (D) (thickness: 250μm) by T-die molding using a hanger manifold T-die film melt extrudingpress machine (stationary type manufactured by GSI Creos Corp.) equippedwith a screw having a screw diameter of 20 mm, a compression ratio of3.1, and L/D=30 under the following conditions.

The type, composition, Mw, Mw/Mn, hydrogenation degree (%),isomerization ratio (%), and melting point (° C.) of the hydrogenatedring-open polymer forming the monolayer sheet (D) are shown in Table 7.

<Molding Conditions> Die lip: 0.8 mm

Molten resin temperature: 170° C.

Width of T-die: 300 mm

Cooling roller: 100° C.Casting roll: 110° C.

A process sheet (4) was prepared in the same manner as in Example 21,except that the monolayer sheet (D) was used instead of the monolayersheet (A) and the blister molding temperature was 105° C. The resultingprocess sheet (4) was molded in the same manner as in Example 21 toobtain a PTP (4). Oil resistance of the resulting PTP (4) and blistermoldability of the pockets of the PTP (4) were evaluated. The resultsare shown in Table 8.

Table 8 also shows the steam barrier properties of the monolayer sheet(D).

Example 25 Sheet Forming

The pellets (E) were molded into a monolayer sheet (E) (thickness: 250μm) by T-die molding using a hanger manifold T-die film melt extrudingpress machine (stationary type manufactured by GSI Creos Corp.) equippedwith a screw having a screw diameter of 20 mm, a compression ratio of3.1, and L/D=30 under the following conditions.

The type, composition, Mw, Mw/Mn, hydrogenation degree (%),isomerization ratio (%), and melting point (° C.) of the hydrogenatedring-open polymer forming the monolayer sheet (E) are shown in Table 7.

<Molding Conditions> Die lip: 0.8 mm

Molten resin temperature: 180° C.

Width of T-die: 300 mm

Cooling roller: 120° C.Casting roll: 130° C.

A process sheet (5) was prepared in the same manner as in Example 21,except for using the monolayer sheet (E) instead of the monolayer sheet(A). Steam barrier properties of the monolayer sheet (E), oil resistanceof the resulting process sheet (5) and the PTP (5), and blistermoldability of the pockets of the PTP (5) were evaluated. The resultsare shown in Table 8.

Table 8 also shows the steam barrier properties of the monolayer sheet(E).

Example 26 Sheet Forming

The pellets (F) were molded into a monolayer sheet (F) (thickness: 250μm) by T-die molding using a hanger manifold T-die film melt extrudingpress machine (stationary type manufactured by GSI Creos Corp.) equippedwith a screw having a screw diameter of 20 mm, a compression ratio of3.1, and L/D=30 under the following conditions.

The type, composition, Mw, Mw/Mn, hydrogenation degree (%),isomerization ratio (%), and melting point (° C.) of the hydrogenatedring-open polymer forming the monolayer sheet (F) are shown in Table 7.

<Molding Conditions> Die lip: 0.8 mm

Molten resin temperature: 180° C.

Width of T-die: 300 mm

Cooling roller: 120° C.Casting roll: 130° C.

A process sheet (6) was prepared in the same manner as in Example 21,except for using the monolayer sheet (F) instead of the monolayer sheet(A). The resulting process sheet (6) was molded in the same manner as inExample 21 to obtain a PTP (6). Steam barrier properties of themonolayer sheet (F), oil resistance of the resulting process sheet (6),and the blister processability of the pockets of the PTP (6) wereevaluated. The results are shown in Table 8.

Table 8 also shows the steam barrier properties of the monolayer sheet(F).

Example 27 Sheet Forming

The pellets (G) were molded into a monolayer sheet (G) (thickness: 250μm) by T-die molding using a hanger manifold T-die film melt extrudingpress machine (stationary type manufactured by GSI Creos Corp.) equippedwith a screw having a screw diameter of 20 mm, a compression ratio of3.1, and L/D=30 under the following conditions.

The type, composition, Mw, Mw/Mn, hydrogenation degree (%),isomerization ratio (%), and melting point (° C.) of the hydrogenatedring-open polymer forming the monolayer sheet (G) are shown in Table 7.

<Molding Conditions> Die lip: 0.8 mm

Molten resin temperature: 180° C.

Width of T-die: 300 mm

Cooling roller: 120° C.Casting roll: 130° C.

A process sheet (7) and a PTP (7) were prepared in the same manner as inExample 21, except for using the monolayer sheet (G) instead of themonolayer sheet (A). Steam barrier properties of the monolayer sheet (G)and blister processability of the pockets of the resulting process sheet(7) and the PTP (7) were evaluated. The results are shown in Table 8.

Table 8 also shows the steam barrier properties of the monolayer sheet(G).

Example 28

A non-stretched polypropylene film (Pylene Film-CT, manufactured byToyobo Co., Ltd. thickness: 30 μm) was attached to one side of themonolayer film (C2) via a urethane adhesive at 70° C. to obtain amultilayer film (1) (total thickness: 250 μm).

A process sheet (8) was prepared in the same manner as in Example 21,except for using the multilayer sheet (1) instead of the monolayer sheet(A). The resulting process sheet (8) was molded in the same manner as inExample 21 to obtain a PTP (8) with the non-stretched polypropylene filmlayer being disposed on the convex side of the PTP (8). Oil resistanceof the resulting process sheet (8) and blister moldability of thepockets of the PTP (8) were evaluated. The results are shown in Table 9.

Table 9 also shows steam barrier properties of the multilayer sheet (1).

Example 29)

The pellets (C) and a linear low density polyethylene having a meltingpoint of 126° C. and a density of 0.937 g/cm³ (UMERIT 4040F manufacturedby Ube Industries, Ltd.) were molded into a multilayer sheet consistingof the pellet (C) and the linear low density polyethylene (thickness:pellet (C): 165 μm, linear low density polyethylene: 50 μm, total: 215μm) by T-die molding using a hanger manifold T-die film melt extrudingpress machine (stationary type manufactured by GSI Creos Corp.) equippedwith a screw having a screw diameter of 20 mm, a compression ratio of3.1, and L/D=30 under the following conditions.

<Molding Conditions> Die lip: 0.8 mm

(Pellet (C)) Molten resin temperature: 180° C.(Linear low density polyethylene) Molten resin temperature: 180° C.

Width of T-die: 300 mm

Cooling roller: 110° C.Casting roll: 120° C.

A non-stretched nylon film (Rayfan NO manufactured by Toyobo AdvancedFilm Co., Ltd., thickness: 30 μm) was attached to one side of theresulting multilayer film of pellet (C) and the linear low densitypolyethylene via a urethane adhesive at 70° C. to obtain a multilayerfilm (2) (total thickness: 250 μm).

A process sheet (9) was prepared in the same manner as in Example 21,except for using the multilayer sheet (2) instead of the monolayer sheet(A). The resulting process sheet (9) was molded in the same manner as inExample 21 to obtain a PTP (9) with the non-stretched nylon film layerbeing disposed on the convex side of the PTP (9). Oil resistance of theresulting process sheet (9) and blister moldability of the pockets ofthe PTP (9) were evaluated. The results are shown in Table 9.

Table 9 also shows steam barrier properties of the multilayer sheet (2).

Example 30

A non-stretched polypropylene film (Pylene Film-CT, manufactured byToyobo Co., Ltd. thickness: 30 μm) was attached to both sides of themonolayer film (C3) via a urethane adhesive at 70° C. to obtain amultilayer film (3) (total thickness: 250 μm).

A process sheet (10) was prepared in the same manner as in Example 21,except for using the multilayer sheet (3) instead of the monolayer sheet(A). The resulting process sheet (10) was molded in the same manner asin Example 21 to obtain a PTP (10). Steam barrier properties of themultilayer sheet (3), oil resistance of the resulting process sheet(10), and blister moldability of the pockets of the PTP (10) wereevaluated. The results are shown in Table 9.

Table 9 also shows steam barrier properties of the multilayer sheet (3).

Comparative Example 12 Sheet Forming

The pellets (H) were molded into a monolayer sheet (H1) (thickness: 250μm) and a monolayer sheet (H2) (thickness: 180 μm) by T-die moldingusing a hanger manifold T-die film melt extruding press machine(stationary type manufactured by GSI Creos Corp.) equipped with a screwhaving a screw diameter of 20 mm, a compression ratio of 2.5, and L/D=30under the following conditions.

The type, composition, Mw, Mw/Mn, hydrogenation degree (%),isomerization ratio (%), and melting point (° C.) of the hydrogenatedring-open polymer forming the monolayer sheet (H1) are shown in Table 7.

<Molding Conditions> Die lip: 0.8 mm

Molten resin temperature: 230° C.

Width of T-die: 300 mm

Cooling roller: 85° C.Casting roll: 95° C.

A process sheet (11) was prepared in the same manner as in Example 21,except that the monolayer sheet (H1) was used instead of the monolayersheet (A) and the blister molding temperature was 110° C. The resultingprocess sheet (11) was molded in the same manner as in Example 21 toobtain a PTP (11). Oil resistance of the resulting PTP (11) and blistermoldability of the pockets of the PTP (11) were evaluated. The resultsare shown in Table 8.

Table 8 also shows steam barrier properties of the monolayer sheet (H1).

Comparative Example 13 Sheet Forming

The pellets (I) were molded into a monolayer sheet (I) (thickness: 250μm) by T-die molding using a hanger manifold T-die film melt extrudingpress machine (stationary type manufactured by GSI Creos Corp.) equippedwith a screw having a screw diameter of 20 mm, a compression ratio of3.1, and L/D=30 under the following conditions.

The type, composition, Mw, Mw/Mn, hydrogenation degree (%),isomerization ratio (%), and melting point (° C.) of the hydrogenatedring-open polymer forming the monolayer sheet (I) are shown in Table 7.

<Molding Conditions> Die lip: 0.8 mm

Molten resin temperature: 150° C.

Width of T-die: 300 mm

Cooling roller: 80° C.Casting roll: 90° C.

A process sheet (12) was prepared in the same manner as in Example 21,except that the monolayer sheet (I) was used instead of the monolayersheet (A) and the blister molding temperature was 95° C. The resultingprocess sheet (12) was molded in the same manner as in Example 21 toobtain a PTP (12).

Oil resistance of the resulting process sheet (12) and blistermoldability of the pockets of the PTP (12) were evaluated. The resultsare shown in Table 8.

Table 8 also shows steam barrier properties of the monolayer sheet (I).

Comparative Example 14 Sheet Forming

The pellets (J) were molded into a monolayer sheet (J) (thickness: 250μm) by T-die molding using a hanger manifold T-die film melt extrudingpress machine (stationary type manufactured by GSI Creos Corp.) equippedwith a screw having a screw diameter of 20 mm, a compression ratio of3.1, and L/D=30 under the following conditions.

The type, composition, Mw, Mw/Mn, hydrogenation degree (%),isomerization ratio (%), and melting point (° C.) of the hydrogenatedring-open polymer forming the monolayer sheet (J) are shown in Table 7.

<Molding Conditions> Die lip: 0.8 mm

Molten resin temperature: 310° C.

Width of T-die: 300 mm

Cooling roller: 220° C.Casting roll: 230° C.

The experiment of preparing a process sheet was carried out in the samemanner as in Example 21, except that the monolayer sheet (J) was usedinstead of the monolayer sheet (A) and the blister molding temperatureof 260° C., which is around the upper limit of the molding machine, wasemployed. The pocket portions were not dented, failing to produce aprocess sheet.

Table 8 shows steam barrier properties of the monolayer sheet (J).

Comparative Example 15

A multilayer sheet (4), a process sheet (13) and a PTP (13) wereprepared in the same manner as in Example 21, except for using themonolayer sheet (H2) instead of the monolayer sheet (A).

Oil resistance of the resulting process sheet (13) and blistermoldability of the pockets of the PTP (13) were evaluated. The resultsare shown in Table 9.

Table 9 also shows steam barrier properties of the multilayer sheet (4).

TABLE 7 Hydrogenated ring-open polymer Monolayer HydrogenationIsomerization Melting sheet No. Composition Mw Mw/Mn rate (%) degree (%)point (° C.) Example 21 A 1 NB 100 82200 2.9 99.9 5 140 22 B 11 NB/MNB =98/2 100000 2.9 99.9 8 136 23 C1 12 NB/MNB = 96/4 80000 2.9 99.9 8 13324 D 14 NB/MNB = 91/9 98800 3.8 99.9 7 114 25 E 13 NB/DCP = 99/1 1600001.8 99.9 0 139 26 F 15 NB/DCP = 96/4 81300 3.8 99.9 9 134 27 G 8 NB 10064200 1.3 99.75 0 143 Comparative 12 H1 19 DCP 100 53000 3.6 99.9 — —Example 13 I 17 NB/TCD = 89/11 315000 4.9 99.0 9 100 14 J 7 DCP 100 — —— — 273

TABLE 8 Steam barrier properties of Oil resistance Blister moldabilityMonolayer monolayer sheet (g/(m² · 24 h)) Process of process (number ofcrushed sheet 40° C. × 90% RH 50° C. × 90% RH sheet sheet PTP pockets)Example 21 A 0.07 0.21 1 After 6 days 1 5 22 B 0.12 0.25 2 After 6 days2 1 23 C1 0.15 0.28 3 After 5 days 3 0 24 D 0.21 0.36 4 After 5 days 4 025 E 0.11 0.26 5 After 8 days 5 4 26 F 0.17 0.30 6 After 4 days 6 0 27 G0.09 0.23 7 After 4 days 7 10 Comparative 12 H1 0.43 0.80 11 Within 1hour 11 3 Example 13 I 0.31 0.64 12 After 7 days 12 83 14 J 0.40 0.70 —— — —

TABLE 9 Blister Steam barrier properties of moldability Multilayer Layermultilayer sheet (g/(m² · 24 h)) Process Oil resistance of (number ofsheet constitution 40° C. × 90% RH 50° C. × 90% RH sheet process sheetPTP crushed pockets) Example 28 1 C2/PP 0.07 0.21 8 No change for 8 0 10days or more 29 2 Ny/C/PE 0.12 0.25 9 No change for 9 0 10 days or more30 3 PP/C3/PP 0.15 0.28 10 No change for 10 0 10 days or moreComparative 15 4 PP/H2/PP 0.45 1.00 13 No change for 13 2 Example 10days or more PP = Polypropylene, PE = Polyethylene, Ny = Nylon

As can be seen from Tables 8 and 9, the blister molded sheets ofExamples 21 to 27 and Examples 28 to 30 (monolayer sheets (A) to (G) andmultilayer sheets (1) to (3)) had a moisture permeability of 0.21g/(m²·24 h) or less at 40° C. and 90% RH, and 0.36 g/(m²·24 h) or lessat 50° C. and 90% RH, showing excellent steam barrier properties,particularly at a high temperature. On the other hand, the blistermolded sheets of Comparative Examples 12 to 15 (monolayer sheets (H1) to(J) and multilayer sheet (4)) had a moisture permeability of 0.31 to0.45 g/(m²·24 h) at 40° C. and 90% RH, and 0.64 to 1.0 g/(m²·24 h) at50° C. and 90% RH, showing inferior steam barrier properties,particularly at a high temperature.

The number of crushed pockets in the PTPs (1) to (10) of Examples 21 to27 and Examples 28 to 30 and PTPs (11) and (13) of Comparative Examples12 and 15 was 10 out of 100 pockets, showing excellent blistermoldability. On the other hand, in the PTP (12) of Comparative Example13, 83 pockets out of 100 pockets were crushed, indicating poor blistermoldability.

The process sheets (1) to (10) of Examples 21 to 27 and Examples 28 to30 and the process sheets (12) of Comparative Example 2 required fourdays or more before being whitened, showing excellent oil resistance. Onthe other hand, the process sheet (11) of Comparative Example 12 waswhitened within one hour in the oil resistance evaluation test,indicating poor oil resistance.

The monolayer sheet (J) had too high a melting point to be blistermolded.

Based on the above results, the blister molding sheet and theblister-molded article of the present invention were confirmed to haveexcellent steam barrier properties particularly at a high temperature,superior blister moldability, and good oil resistance.

Film Production Example 1

The pellets (A) obtained in Pellet Production Example 1 were molded intoa monolayer film (A) (thickness: 30 μm) by T-die molding using a hangermanifold T-die film melt extruding press machine (stationary typemanufactured by GSI Creos Corp.) equipped with a screw having a screwdiameter of 20 mm, a compression ratio of 3.1, and L/D=30 under thefollowing conditions.

<Molding Conditions> Die lip: 0.8 mm

Molten resin temperature: 180° C.

Width of T-die: 300 mm

Cooling roller: 120° C.Casting roll: 130° C.

Film Production Example 2

The pellets (B) obtained in Pellet Production Example 2 were molded intoa monolayer film (B) (thickness: 30 μm) by T-die molding using a hangermanifold T-die film melt extruding press machine (stationary typemanufactured by GSI Creos Corp.) equipped with a screw having a screwdiameter of 20 mm, a compression ratio of 3.1, and L/D=30 under thefollowing conditions.

<Molding Conditions> Die lip: 0.8 mm

Molten resin temperature: 180° C.

Width of T-die: 300 mm

Cooling roller: 120° C.Casting roll: 130° C.

Film Production Example 3

The pellets (C) obtained in Pellet Production Example 3 were molded intoa monolayer film (C) (thickness: 30 μm) by T-die molding using a hangermanifold T-die film melt extruding press machine (stationary typemanufactured by GSI Creos Corp.) equipped with a screw having a screwdiameter of 20 mm, a compression ratio of 3.1, and L/D=30 under thefollowing conditions.

<Molding Conditions> Die lip: 0.8 mm

Molten resin temperature: 180° C.

Width of T-die: 300 mm

Cooling roller: 120° C.Casting roll: 130° C.

Film Production Example 4

The pellets (D) obtained in Pellet Production Example 4 were molded intoa monolayer film (D) (thickness: 30 μm) by T-die molding using a hangermanifold T-die film melt extruding press machine (stationary typemanufactured by GSI Creos Corp.) equipped with a screw having a screwdiameter of 20 mm, a compression ratio of 3.1, and L/D=30 under thefollowing conditions.

<Molding Conditions> Die lip: 0.8 mm

Molten resin temperature: 170° C.

Width of T-die: 300 mm

Cooling roller: 100° C.Casting roll: 110° C.

Film Production Example 5

The pellets (E) obtained in Pellet Production Example 5 were molded intoa monolayer film (E) (thickness: 30 μm) by T-die molding using a hangermanifold T-die film melt extruding press machine (stationary typemanufactured by GSI Creos Corp.) equipped with a screw having a screwdiameter of 20 mm, a compression ratio of 3.1, and L/D=30 under thefollowing conditions.

<Molding Conditions> Die lip: 0.8 mm

Molten resin temperature: 180° C.

Width of T-die: 300 mm

Cooling roller: 120° C.Casting roll: 130° C.

Film Production Example 6

The pellets (F) obtained in Pellet Production Example 6 were molded intoa monolayer film (F) (thickness: 30 μm) by T-die molding using a hangermanifold T-die film melt extruding press machine (stationary typemanufactured by GSI Creos Corp.) equipped with a screw having a screwdiameter of 20 mm, a compression ratio of 3.1, and L/D=30 under thefollowing conditions.

<Molding Conditions> Die lip: 0.8 mm

Molten resin temperature: 180° C.

Width of T-die: 300 mm

Cooling roller: 120° C.Casting roll: 130° C.

Film Production Example 7

The pellets (G) obtained in Pellet Production Example 7 were molded intoa monolayer film (G1) (thickness: 30 μm) and a monolayer film (G2)(thickness: 50 μm) by T-die molding using a hanger manifold T-die filmmelt extruding press machine (stationary type manufactured by GSI CreosCorp.) equipped with a screw having a screw diameter of 20 mm, acompression ratio of 3.1, and L/D=30 under the following conditions.

<Molding Conditions> Die lip: 0.8 mm

Molten resin temperature: 180° C.

Width of T-die: 300 mm

Cooling roller: 120° C.Casting roll: 130° C.

Film Production Example 8

0.1 part by weight of Antioxidant A was added to 100 parts by weight ofthe hydrogenated ring-open polymer (9) obtained in Comparative Example 3and the mixture was kneaded using a twin-screw kneader (TEM35Bmanufactured by Toshiba Machine Co., Ltd.) to obtain pellets (K).

(Film Forming)

The pellets (K) were molded into a monolayer film (H) (thickness: 30 μm)by T-die molding using a hanger manifold T-die film melt extruding pressmachine (stationary type manufactured by GSI Creos Corp.) equipped witha screw having a screw diameter of 20 mm, a compression ratio of 2.5,and L/D=30 under the following conditions.

<Molding Conditions> Die lip: 0.8 mm

Molten resin temperature: 250° C.

Width of T-die: 300 mm

Cooling roller: 125° C.Casting roll: 135° C.

Film Production Example 9

The pellets (I) obtained in Pellet Production Example 9 were molded intoa monolayer film (I) (thickness: 30 μm) by T-die molding using a hangermanifold T-die film melt extruding press machine (stationary typemanufactured by GSI Creos Corp.) equipped with a screw having a screwdiameter of 20 mm, a compression ratio of 3.1, and L/D=30 under thefollowing conditions.

<Molding Conditions> Die lip: 0.8 mm

Molten resin temperature: 150° C.

Width of T-die: 300 mm

Cooling roller: 80° C.Casting roll: 90° C.

Film Production Example 10

The pellets (J) obtained in Pellet Production Example 10 were moldedinto a monolayer film (J) (thickness: 30 μm) by T-die molding using ahanger manifold T-die film melt extruding press machine (stationary typemanufactured by GSI Creos Corp.) equipped with a screw having a screwdiameter of 20 mm, a compression ratio of 3.1, and L/D=30 under thefollowing conditions. A high temperature was necessary for molding thepellets (J), and coloration due to resin burning was observed on theresulting monolayer film.

<Molding Conditions> Die lip: 0.8 mm

Molten resin temperature: 310° C.

Width of T-die: 300 mm

Cooling roller: 220° C.Casting roll: 230° C.

The weight average molecular weight, molecular weight distribution,melting point, and isomerization ratio of the monolayer films (A) to (J)obtained in Film Production Examples 1 to 10 are shown in Table 10.

TABLE 10 Hydrogenated ring-open polymer Monolayer HydrogenationIsomerization Melting film No. Composition Mw Mw/Mn rate (%) degree (%)point (° C.) Film 1 A 1 NB 100 82200 2.9 99.9 5 140 Production 2 B 11NB/MNB = 98/2 100000 2.9 99.9 8 136 Example 3 C 12 NB/MNB = 96/4 800002.9 99.9 8 133 4 D 14 NB/MNB = 91/9 98800 3.8 99.9 7 114 5 F 13 NB/DCP =99/1 160000 1.8 99.9 0 139 6 E 15 NB/DCP = 96/4 81300 3.8 99.9 9 134 7 G8 NB 100 64200 1.3 99.75 0 143 8 H 9 MTD/DCP = 80/20 55000 3.1 99.9 — —9 I 18 NB/TCD = 89/11 315000 4.9 99.0 9 100 10 J 7 DCP 100 — — — — 273

Example 31

The monolayer film (A) was attached to one side of an ethylene-vinylalcohol copolymer film with an ethylene content of 32% (Eval Fmanufactured by Kuraray Co., Ltd. thickness: 15 μm) via a urethaneadhesive (Takenate/Takelac manufactured by Mitsui Takeda Chemical Co.,Ltd.) at 70° C. to obtain a multilayer film (1) (total thickness: 50μm). The steam barrier properties and oil resistance of the resultingmultilayer film (1) were evaluated. The results are shown in Table 11.

The resulting multilayer film (1) was cut into 20 cm squares. Two sheetsof the square cut film were layered with the ethylene-vinyl alcoholcopolymer film layers being face to face, and three sides wereheat-sealed with a hot melt adhesive (Aron Melt PPET manufactured byToagosei Co., Ltd) at 190° C. and 0.2 MPa for two seconds using aheat-sealing tester (TP-701-B manufactured by Tester Industrial Co,Ltd.) to obtain a bag (1).

The bag (1) was filled with 70 ml of 5% brine and the open side washeat-sealed in the same manner as above to obtain a brine pack (1). Thebrine pack (1) had no defects such as breaking, cracks, inadequatesealing, and the like. Impact resistance of the brine pack (1) wasevaluated. The results are shown in Table 11.

Example 32

A multilayer film (2), a bag (2), and a brine pack (2) were prepared inthe same manner as in Example 31, except for using the monolayer film(B) instead of the monolayer film (A). The brine pack (2) had no defectssuch as breaking, cracks, inadequate sealing, and the like.

Steam barrier properties and oil resistance of the resulting multilayerfilm (2) and impact resistance of the brine pack (2) were evaluated. Theresults are shown in Table 11.

Example 33

A multilayer film (3), a bag (3), and a brine pack (3) were prepared inthe same manner as in Example 31, except for using the monolayer film(C) instead of the monolayer film (A). The brine pack (3) had no defectssuch as breaking, cracks, inadequate sealing, and the like.

Steam barrier properties and oil resistance of the resulting multilayerfilm (3) and impact resistance of the brine pack (3) were evaluated. Theresults are shown in Table 11.

Example 34

A multilayer film (4), a bag (4), and a brine pack (4) were prepared inthe same manner as in Example 31, except for using the monolayer film(D) instead of the monolayer film (A). The brine pack (4) had no defectssuch as breaking, cracks, inadequate sealing, and the like.

Steam barrier properties and oil resistance of the resulting multilayerfilm (4) and impact resistance of the brine pack (4) were evaluated. Theresults are shown in Table 11.

Example 35

A multilayer film (5), a bag (5), and a brine pack (5) were prepared inthe same manner as in Example 35, except for using the monolayer film(E) instead of the monolayer film (A). The brine pack (5) had no defectssuch as breaking, cracks, inadequate sealing, and the like.

Steam barrier properties and oil resistance of the resulting multilayerfilm (5) and impact resistance of the brine pack (5) were evaluated. Theresults are shown in Table 11.

Example 36

A multilayer film (6), a bag (6), and a brine pack (6) were prepared inthe same manner as in Example 31, except for using the monolayer film(F) instead of the monolayer film (A). The brine pack (6) had no defectssuch as breaking, cracks, inadequate sealing, and the like.

Steam barrier properties and oil resistance of the resulting multilayerfilm (6) and impact resistance of the brine pack (6) were evaluated. Theresults are shown in Table 11.

Example 37

The pellets (C) and a linear low density polyethylene (UMERIT 4040Fmanufactured by Ube Industries, Ltd.) were molded into a multilayer film(7), consisting of the pellet (C) and the linear low densitypolyethylene (thickness: pellet (C): 30 μm, linear low densitypolyethylene: 20 μm, total: 50 μm) by T-die molding using a hangermanifold T-die film melt extruding press machine (stationary typemanufactured by GSI Creos Corp.) equipped with a screw having a screwdiameter of 20 mm, a compression ratio of 3.1, and L/D=30 under thefollowing conditions.

<Molding Conditions> Die lip: 0.8 mm

(Pellet (C)) Molten resin temperature: 180° C.(Linear low density polyethylene) Molten resin temperature: 180° C.

Width of T-die: 300 mm

Cooling roller: 110° C.Casting roll: 120° C.

The steam barrier properties and oil resistance of the resultingmultilayer film (7) were evaluated. The results are shown in Table 11.

The resulting multilayer film (7) was cut into 20 cm squares. Two sheetsof the square cut film were layered with the linear low densitypolyethylene layers being face to face, and three sides were heat-sealedat 190° C. and 0.2 MPa for two seconds using a heat-sealing tester(TP-701-B manufactured by Tester Industrial Co, Ltd.) to obtain a bag(7).

The bag (7) was filled with 70 ml of 5% brine and the open side washeat-sealed in the same manner as above to obtain a brine pack (7). Thebrine pack (7) had no defects such as breaking, cracks, inadequatesealing, and the like. Impact resistance of the brine pack (7) wasevaluated. The results are shown in Table 11.

Example 38

A biaxial stretched nylon film (Harden Film manufactured by Toyobo Co.,Ltd. thickness: 15 μm) was attached to one side of the monolayer film(C) obtained above via a urethane adhesive (Takenate/Takelacmanufactured by Mitsui Takeda Chemical Co., Ltd.) at 70° C. to obtain amultilayer film (8) (total thickness: 50 μm). The steam barrierproperties and oil resistance of the resulting multilayer film (8) wereevaluated. The results are shown in Table 11.

The resulting multilayer film (8) was cut into 20 cm squares. Two sheetsof the square cut film were layered with the layers of pellets (C) beingface to face, and three sides were heat-sealed at 190° C. and 0.2 MPafor two seconds using a heat-sealing tester (TP-701-B manufactured byTester Industrial Co, Ltd.) to obtain a bag (8).

The bag (8) was filled with 70 ml of 5% brine and the open side washeat-sealed in the same manner as above to obtain a brine pack (8). Thebrine pack (8) had no defects such as breaking, cracks, inadequatesealing, and the like. Impact resistance of the brine pack (8) wasevaluated. The results are shown in Table 11.

Example 39

A multilayer film (9), a bag (9), and a brine pack (9) were prepared inthe same manner as in Example 38, except for using the monolayer film(G1) instead of the monolayer film (C). The brine pack (9) had nodefects such as breaking, cracks, inadequate sealing, and the like.

Steam barrier properties and oil resistance of the resulting multilayerfilm (9) and impact resistance of the brine pack (9) were evaluated. Theresults are shown in Table 11.

Comparative Example 16

A multilayer film (10), a bag (10), and a brine pack (10) were preparedin the same manner as in Example 31, except for using the monolayer film(H) instead of the monolayer film (A). The brine pack (10) had nodefects such as breaking, cracks, inadequate sealing, and the like.

Steam barrier properties and oil resistance of the resulting multilayerfilm (10) and impact resistance of the brine pack (10) were evaluated.The results are shown in Table 11.

Comparative Example 17

A multilayer film (11), a bag (11), and a brine pack (11) were preparedin the same manner as in Example 31, except for using the monolayer film(I) instead of the monolayer film (A). The brine pack (11) had nodefects such as breaking, cracks, inadequate sealing, and the like.

Steam barrier properties and oil resistance of the resulting multilayerfilm (11) and impact resistance of the brine pack (12) were evaluated.The results are shown in Table 11.

Comparative Example 18

A multilayer film (12) was prepared in the same manner as in Example 31,except for using the monolayer film (J) instead of the monolayer film(A). A bag (12) and a brine pack (12) were also obtained. The brine pack(12) had no defects such as breaking, cracks, inadequate sealing, andthe like.

The steam barrier properties and oil resistance of the resultingmultilayer film (12) were evaluated. The results are shown in Table 11.

Comparative Example 19

A bag (13) and a brine pack (13) were prepared in the same manner as inExample 31, except for using the monolayer film (G2) instead of themultilayer film (1). The brine pack (13) had no defects such asbreaking, cracks, inadequate sealing, and the like.

Steam barrier properties and oil resistance of the resulting monolayerfilm (G2) and impact resistance of the brine pack (13) were evaluated.The results are shown in Table 11.

Symbols shown in Table 11 have the following meanings.

EV: Ethylene-vinyl alcohol copolymer film layerAD: Urethane adhesive layerA to F, G1, G2, and H to K: Hydrogenated norbornene ring-open polymerlayerLPE: Linear low density polyethylene layerNY: Biaxial stretched nylon film layer

TABLE 11 Steam barrier Impact Layer properties Brine resistance Filmconstitution (g/(m² · 24 h) bag of brine bag Oil resistance Example 31Multilayer film (1) EV/AD/A 1.7 1 11 Whitened after 6 days 32 Multilayerfilm (2) EV/AD/B 1.8 2 4 Whitened after 6 days 33 Multilayer film (3)EV/AD/C 1.8 3 1 Whitened after 5 days 34 Multilayer film (4) EV/AD/D 2.54 0 Whitened after 5 days 35 Multilayer film (5) EV/AD/E 1.7 5 6Whitened after 8 days 36 Multilayer film (6) EV/AD/F 2 6 2 Whitenedafter 4 days 37 Multilayer film (7) C/LPE 1.9 7 1 Whitened after 5 days38 Multilayer film (8) NY/AD/C 2 8 0 Whitened after 5 days 39 Multilayerfilm (9) NY/AD/G1 1.7 9 10 Whitened after 4 days Comparative 16Multilayer film (10) EV/AD/H 5 10 58 Whitened within one hour Example 17Multilayer film (11) EV/AD/I 4.1 11 46 Whitened after 7 days 18Multilayer film (12) EV/AD/J 3.3 12 72 Whitened after 8 days 19Monolayer film (G2) G2 1.1 13 97 Whitened after 4 days

As shown in Table 11, the multilayer films (multilayer articles) ofExamples 31 to 39 and the monolayer film of Comparative Example 19showed excellent steam barrier properties. On the other hand, themultilayer films of Comparative Examples 16 to 18 exhibited poor steambarrier properties.

The multilayer films of Examples 31 to 39, the multilayer films ofComparative Examples 17 and 18, and the monolayer film of ComparativeExample 19 exhibited excellent oil resistance. On the other hand, themultilayer film of Comparative Example 16 exhibited poor oil resistance.

Furthermore, the brine packs (packing material) of Examples 31 to 39exhibited excellent impact resistance. On the other hand, the brine packof Comparative Examples 16 to 19 exhibited poor impact resistance.

Example 40

The multilayer film (1) obtained above was cut into two A4 size sheets.Two sheets were layered with the ethylene-vinyl alcohol copolymer filmlayers being face to face, and the four sides were heat-sealed with ahot melt adhesive (Aron Melt PPET manufactured by Toagosei Co., Ltd) at190° C. and 0.2 MPa for two seconds using a heat-sealing tester(TP-701-B manufactured by Tester Industrial Co, Ltd.) to obtain a bag.The bag was put into and left in boiling water for 30 minutes and a 15cm square in the center was cut to obtain a boiled film (1).

Gas barrier properties of the multilayer film (1) and the boiled film(1) were evaluated. The results are shown in Table 12.

Example 41

A boiled film (2) was obtained in the same manner as in Example 40,except for using the multilayer film (3) instead of the multilayer film(1).

Gas barrier properties of the multilayer film (3) and the boiled film(2) were evaluated. The results are shown in Table 12.

Example 42

A boiled film (3) was obtained in the same manner as in Example 40,except for using the multilayer film (6) instead of the multilayer film(1).

Gas barrier properties of the multilayer film (6) and the boiled film(3) were evaluated. The results are shown in Table 12.

Comparative Example 20

A boiled film (4) was obtained in the same manner as in Example 40,except for using the multilayer film (10) instead of the multilayer film(1).

Gas barrier properties of the multilayer film (10) and the boiled film(4) were evaluated. The results are shown in Table 12.

Comparative Example 21

A boiled film (5) was obtained in the same manner as in Example 40,except for using the multilayer film (11) instead of the multilayer film(1).

Gas barrier properties of the multilayer film (11) and the boiled film(5) were evaluated. The results are shown in Table 12.

Comparative Example 22

A multilayer film (13) and a boiled film (6) were obtained in the samemanner as in Example 40, except for using a biaxial stretchedpolypropyrene film (Pylene Film OT manufactured by Toyobo Co., Ltd.thickness: 30 μm) instead of the multilayer film (1).

Gas barrier properties of the resulting multilayer film (13) and theboiled film (6) were evaluated. The results are shown in Table 12.

TABLE 12 Gas barrier properties Gas barrier properties Multilayer Layerof multilayer film of boiled film film constitution (cm⁻³ · m⁻² · day⁻¹· atm⁻¹) Boiled film (cm⁻³ · m⁻² · day⁻¹ · atm⁻¹) Example 40 1 EV/AD/A0.32 1 0.39 41 3 EV/AD/C 0.33 2 0.41 42 6 EV/AD/F 0.35 3 0.42Comparative 20 10 EV/AD/H 0.34 4 3.80 Example 21 11 EV/AD/J 0.34 5 3.1022 13 EV/AD/PP 0.32 6 7.00

As shown in Table 12, the multilayer films having a gas barrier resinlayer of Examples 40 to 42 showed excellent gas barrier properties bothbefore and after the boiling treatment. On the other hand, themultilayer films having a gas barrier resin layer of ComparativeExamples 20 to 22 showed excellent gas barrier properties before theboiling treatment, but poor gas barrier properties after the boilingtreatment.

Example 43

0.1 part by weight of an antioxidant(tetrakis[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane(Irganox 1010 manufactured by Ciba Geigy)) was added to 100 parts byweight of the hydrogenated ring-open polymer (1) obtained in Example 1and the mixture was kneaded using a twin-screw kneader (TEM35manufactured by Toshiba Machine Co., Ltd.) to obtain a pelletized resincomposition (A2).

(Fabrication of Blow-Molded Container)

A preform was prepared from the above pellets using a stretching blowmolding machine (manufactured by Nissei ASB Machine Co., Ltd.) byinjection molding at a cylinder temperature of 200° C. and an injectionmold die temperature of 60° C. Next, the preform was processed by blowmolding at a preform heating pot temperature of 100° C., a blowingpressure of 0.5 MPa, and a blow die temperature of 60° C. to obtain amonolayer stretched blow-molded container (A3) with a lengthwisestretching magnification y of 2.3 times, a horizontal stretchingmagnification x of 2.1 times, and dimensions of 60 mm (depth)×60 mm(width)×180 mm (height)×1 mm (thickness).

A plate (A4) with dimensions of 50 mm×100 mm×1 mm was prepared from theblow-molded container (A3) by cutting the container barrel in the shapeof a 50 mm×100 mm rectangle, of which the center was at 60 mm from thebottom. Steam barrier properties and haze of the resulting plate (A4)were measured. The results are shown in Table 13 and Table 14.

Example 44

0.1 part by weight of an antioxidant(tetrakis[methylene3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane(Irganox 1010 manufactured by Ciba Geigy)) was added to 100 parts byweight of the hydrogenated ring-open polymer (10) obtained in Example 10and the mixture was kneaded using a twin-screw kneader (TEM35manufactured by Toshiba Machine Co., Ltd.) to obtain a pelletized resincomposition (B2).

(Fabrication of Blow-Molded Container)

A preform was prepared from the above pellets using a stretching blowmolding machine (manufactured by Nissei ASB Machine Co., Ltd.) byinjection molding at a cylinder temperature of 200° C. and an injectionmold die temperature of 60° C. Next, the preform was processed by blowmolding at a preform heating pot temperature of 100° C., a blowingpressure of 0.5 MPa, and a blow die temperature of 60° C. to obtain amonolayer stretched blow-molded container (B3) with a lengthwisestretching magnification y of 2.3 times, a horizontal stretchingmagnification x of 2.1 times, and dimensions of 60 mm (depth)×60 mm(width)×180 mm (height)×1 mm (thickness).

A plate (B4) with dimensions of 50 mm×100 mm×1 mm was prepared from theblow-molded container (B3) by cutting the container barrel in the shapeof a 50 mm×100 mm rectangle, of which the center was at 60 mm from thebottom. Steam barrier properties and haze of the resulting plate (B4)were measured. The results are shown in Table 13 and Table 14.

Example 45

0.1 part by weight of an antioxidant(tetrakis[methylene3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane(Irganox 1010 manufactured by Ciba Geigy)) was added to 100 parts byweight of the hydrogenated ring-open polymer (5) obtained in Example 5and the mixture was kneaded using a twin-screw kneader (TEM35manufactured by Toshiba Machine Co., Ltd.) to obtain a pelletized resincomposition (C2).

(Fabrication of Blow-Molded Container)

The pellets were molded by injection molding using a stretching blowmolding machine (manufactured by Nissei ASB Machine Co., Ltd.) at acylinder temperature of 210° C. and an injection mold die temperature of60° C., and blow molded at a heating pot temperature of 100° C., ablowing pressure of 1 MPa, and a blow die temperature of 60° C. toobtain a blow-molded container (C3) with a lengthwise stretchingmagnification y of 2.3 times, a horizontal stretching magnification x of2.1 times, and dimensions of 60 mm (depth)×60 mm (width)×180 mm(height)×1 mm (thickness).

A plate (C4) with dimensions of 50 mm×100 mm×1 mm was prepared from theblow-molded container (C3) by cutting the side of the container in theshape of a 50 mmx 100 mm rectangle, of which the center was at 60 mmfrom the bottom. Steam barrier properties and haze of the resultingplate (C4) were measured. The results are shown in Table 13 and Table14.

Example 46

0.1 part by weight of an antioxidant(tetrakis[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane(Irganox 1010 manufactured by Ciba Geigy)) was added to 100 parts byweight of the hydrogenated ring-open polymer (8) obtained in ReferenceExample 1 and the mixture was kneaded using a twin-screw kneader (TEM35manufactured by Toshiba Machine Co., Ltd.) to obtain a pelletized resincomposition (D2).

(Fabrication of Blow-Molded Container)

A preform was prepared from the above pellets using a stretching blowmolding machine (manufactured by Nissei ASB Machine Co., Ltd.) byinjection molding at a cylinder temperature of 200° C. and an injectionmold die temperature of 60° C. Next, the preform was processed by blowmolding at a preform heating pot temperature of 100° C., a blowingpressure of 0.5 MPa, and a blow die temperature of 60° C. to obtain amonolayer stretched blow-molded container (D3) with a lengthwisestretching magnification y of 2.3 times, a horizontal stretchingmagnification x of 2.1 times, and dimensions of 60 mm (depth)×60 mm(width)×180 mm (height)×1 mm (thickness).

A plate (D4) with dimensions of 50 mm×100 mm×1 mm was prepared from theblow-molded container (D3) by cutting the container barrel in the shapeof a 50 mm×100 mm rectangle, of which the center was at 60 mm from thebottom. Steam barrier properties and haze of the resulting plate (D4)were measured. The results are shown in Table 13 and Table 14.

Example 47

0.1 part by weight of an antioxidant(tetrakis[methylene3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane(Irganox 1010 manufactured by Ciba Geigy)) was added to 100 parts byweight of the hydrogenated ring-open polymer (11) obtained in Example 6and the mixture was kneaded using a twin-screw kneader (TEM35manufactured by Toshiba Machine Co., Ltd.) to obtain a pelletized resincomposition (E2).

(Fabrication of Blow-Molded Container)

A preform was prepared from the above pellets using a stretching blowmolding machine (manufactured by Nissei ASB Machine Co., Ltd.) byinjection molding at a cylinder temperature of 200° C. and an injectionmold die temperature of 60° C. Next, the preform was processed by blowmolding at a preform heating pot temperature of 100° C., a blowingpressure of 0.5 MPa, and a blow die temperature of 60° C. to obtain amonolayer stretched blow-molded container (E3) with a lengthwisestretching magnification y of 2.3 times, a horizontal stretchingmagnification x of 2.1 times, and dimensions of 60 mm (depth)×60 mm(width)×180 mm (height)×1 mm (thickness).

A plate (E4) with dimensions of 50 mm×100 mm×1 mm was prepared from theblow-molded container (E3) by cutting the container barrel in the shapeof a 50 mm×100 mm rectangle, of which the center was at 60 mm from thebottom. Steam barrier properties and haze of the resulting plate (E4)were measured. The results are shown in Table 13 and Table 14.

Example 48) Fabrication of Blow-Molded Container

The pellet-like resin composition (E2) obtained in Example 47 andpolyethylene terephthalate (PET: Novapet manufactured by MitsubishiEngineering-Plastics Corporation) were co-injected to obtain amultilayer preform having a PET/resin composition (E2) layerconstitution. The multilayer preform was blow molded using a stretchingblow molding machine (manufactured by Nissei ASB Machine Co., Ltd.) toobtain a blow-molded container (F3) having a layer constitution of outerlayer/inner layer/outer layer=PET/resin composition (E2)/PET (outerlayer/inner layer/outer layer=300 μm/600 μm/100 μm) and dimensions of 60mm (depth)×60 mm (width)×180 mm (height). The injection temperature whenpreparing the preform was 290° C.

A plate (F4) with dimensions of 50 mm×100 mm×1 mm was prepared from theblow-molded container (F3) by cutting the side of the container in theshape of a 50 mmx 100 mm rectangle, of which the center was at 60 mmfrom the bottom. Steam barrier properties and haze of the resultingplate (F4) were measured. The results are shown in Table 13 and Table14.

Example 49 Fabrication of Blow-Molded Container

The pellet-like resin composition (E2) obtained in Example 5, anethylene-vinyl alcohol copolymer with an ethylene content of 32% (EVOH:EVAL F manufactured by Kuraray Co., Ltd.), and, as an adhesive layer, amaleic acid-modified olefin polymer (Modic manufactured by MitsubishiChemical Corp.) were blow molded using a multilayer blow molding machine(manufactured by Tahara Machinery Ltd.) to obtain a stretched multilayerblow-molded container (G3) having a layer constitution of outermostlayer/adhesive layer/gas barrier layer/adhesive layer/innermostlayer=resin composition (E2)/adhesive/EVOH/adhesive/resin composition(E2) (outermost layer/adhesive layer/gas barrier layer/adhesivelayer/innermost layer=500 μm/20 μm/60 μm/20 μm/400 μm) and dimensions of60 mm (depth)×60 mm (width)×180 mm (height).

A plate (G4) with dimensions of 50 mm×100 mm×1 mm was prepared from theblow-molded container (G3) by cutting the container barrel in the shapeof a 50 mm×100 mm rectangle, of which the center is at 60 mm from thebottom. Steam barrier properties and haze of the resulting plate (G4)were measured. The results are shown in Table 13 and Table 14.

Comparative Example 23

An autoclave equipped with a stirrer was charged with 33.4 parts byweight of a 70 wt % 2-norbornene solution in toluene, 2.86 parts byweight of dicyclopentadiene, 0.020 parts by weight of 1-hexene, and 49.3parts by weight of cyclohexane, and the mixture was stirred. Then, asolution containing 0.023 parts by weight ofbis(tricyclohexylphosphine)benzylidyneruthenium (IV) dichloride in 8.6parts by weight of toluene was added, and the reaction was carried outat 60° C. for 30 minutes. The polymerization conversion rate was about100%. The weight average molecular weight (Mw) of the resultingring-open polymer (25) was 81,000, and the molecular weight distribution(Mw/Mn) was 3.6.

(Hydrogenation Reaction)

0.020 parts by weight of ethyl vinyl ether was added to the polymersolution obtained above and the mixture was stirred, followed by ahydrogenation reaction under hydrogen pressure of 1.0 MPa at 150° C. for20 hours. After cooling to room temperature, a suspension of 0.5 partsby weight of activated carbon in 10 parts by weight of cyclohexane wasadded and the mixture was reacted under hydrogen pressure of 1.0 MPa at150° C. for two hours. The reaction mixture was filtered through afilter with a pore diameter of 0.2 μm to remove activated carbon. Thereaction solution was poured into a large amount of isopropanol to causethe polymer to completely precipitate. The precipitate was collected byfiltration. After washing with acetone, the hydrogenated product wasdried in a vacuum dryer at 100° C. under 0.13×10³ Pa for 48 hours toobtain a hydrogenated ring-open polymer (20).

(Properties of Polymer)

The degree of hydrogenation of the resulting hydrogenated ring-openpolymer (20) was 99.9%, the weight average molecular weight (Mw) was85,000, the molecular weight distribution (Mw/Mn) was 3.9, theisomerization ratio was 0%, and the melting point was 101° C.

(Preparation of Resin Composition)

0.1 part by weight of an antioxidant(tetrakis[methylene3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane(Irganox 1010 manufactured by Ciba Geigy)) was added to 100 parts byweight of the hydrogenated ring-open polymer (20) and the mixture waskneaded using a twin-screw kneader to obtain a pelletized resincomposition (H2).

(Fabrication of Blow-Molded Container)

A preform was prepared from the above pellets using a stretching blowmolding machine (manufactured by Nissei ASB Machine Co., Ltd.) byinjection molding at a cylinder temperature of 200° C. and an injectionmold die temperature of 60° C. Next, the preform was processed by blowmolding at a preform heating pot temperature of 100° C., a blowingpressure of 0.5 MPa, and a blow die temperature of 60° C. to obtain amonolayer stretched blow-molded container (H3) with a lengthwisestretching magnification y of 2.3 times, a horizontal stretchingmagnification x of 2.1 times, and dimensions of 60 mm (depth)×60 mm(width)×180 mm (height)×1 mm (thickness).

A plate (H4) with dimensions of 50 mm×100 mm×1 mm was prepared from theblow-molded container (H3) by cutting the container barrel in the shapeof a 50 mm×100 mm rectangle, of which the center was at 60 mm from thebottom. Steam barrier properties and haze of the resulting plate (H4)were measured. The results are shown in Table 13 and Table 14.

Comparative Example 24

0.1 part by weight of an antioxidant(tetrakis[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane(Irganox 1010 manufactured by Ciba Geigy)) was added to 100 parts byweight of the hydrogenated ring-open polymer (9) obtained in ComparativeExample 3 and the mixture was kneaded using a twin-screw kneader (TEM35manufactured by Toshiba Machine Co., Ltd.) to obtain a pelletized resincomposition (12).

(Fabrication of Blow-Molded Container)

A preform was prepared from the above pellets using a stretching blowmolding machine (manufactured by Nissei ASB Machine Co., Ltd.) byinjection molding at a cylinder temperature of 300° C. and an injectionmold die temperature of 120° C. Next, the preform was processed by blowmolding at a preform heating pot temperature of 250° C., a blowingpressure of 0.5 MPa, and a blow die temperature of 120° C. to obtain amonolayer stretched blow-molded container (13) with a lengthwisestretching magnification y of 2.3 times, a horizontal stretchingmagnification x of 2.1 times, and dimensions of 60 mm (depth)×60 mm(width)×180 mm (height)×1 mm (thickness).

A plate (14) with dimensions of 50 mm×100 mm×1 mm was prepared from theblow-molded container (13) by cutting the side of the container in theshape of a 50 mm×100 mm rectangle, of which the center was at 60 mm fromthe bottom. Steam barrier properties and haze of the resulting plate(14) were measured. The results are shown in Table 13 and Table 14.

Comparative Example 25

0.1 part by weight of an antioxidant(tetrakis[methylene3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane(Irganox 1010 manufactured by Ciba Geigy)) was added to 100 parts byweight of the hydrogenated ring-open polymer (16) obtained inComparative Example 5 and the mixture was kneaded using a twin-screwkneader (TEM35 manufactured by Toshiba Machine Co., Ltd.) to obtain apelletized resin composition (J2).

A preform was prepared from the above pellets using a stretching blowmolding machine (manufactured by Nissei ASB Machine Co., Ltd.) byinjection molding at a cylinder temperature of 200° C. and an injectionmold die temperature of 60° C. Next, the preform was processed by blowmolding at a preform heating pot temperature of 100° C., a blowingpressure of 0.5 MPa, and a blow die temperature of 60° C. to obtain amonolayer stretched blow-molded container (J3) with a lengthwisestretching magnification y of 2.3 times, a horizontal stretchingmagnification x of 2.1 times, and dimensions of 60 mm (depth)×60 mm(width)×180 mm (height)×1 mm (thickness).

A plate (J4) with dimensions of 50 mm×100 mm×1 mm was prepared from theblow-molded container (J3) by cutting the container barrel in the shapeof a 50 mm×100 mm rectangle, of which the center is at 60 mm from thebottom. Steam barrier properties and haze of the resulting plate (J4)were measured. The results are shown in Table 13 and Table 14.

TABLE 13 Blow Hydrogenated ring-open polymer molded Melting containerMonomer Hydrogenation Mw/ Isomerization Point Pellet code No. (wt %)rate (%) Mw Mn rate (%) (° C.) Code code Example 43 A3 1 2-NB 99.982,200 2.9 5 140 A1 A2 (100) 44 B3 15 2-NB/DCP 99.9 81,300 3.8 9 134 B1B2 (96/4) 45 C3 5 2-NB 99.9 185,000 4.4 10 136 C1 C2 (100) 46 D3 8 2-NB99.75 64,200 1.3 0 143 D1 D2 (100) 47 E3 11 2-NB/MNB 99.9 100,000 2.9 8136 E1 E2 (98/2) 48 F3 11 2-NB/MNB 99.9 100,000 2.9 8 136 E1 E2 (98/2)49 G3 11 2-NB/MNB 99.9 100,000 2.9 8 136 E1 E2 (98/2) Comparative 23 H320 2-NB/DCP 99.9 85,000 3.9 0 101 H1 H2 Example (89/11) 24 I3 9 DCP — —— — 273 I1 I2 (100) 25 J3 16 MTD/DCP 99.9 55,000 2.9 — Tg = J1 J2(80/20) 140° C.

TABLE 14 Blow molded container Steam barrier Blow moldability Layerconstitution properties Falling standard deviation Haze (thickness: μm)(g/(m² · 24 h)) strength* (σ) Oil resistance (%) Example 43 A2 0.02328/30 0.05 mm Not whitened ≦20 (1000) 44 B2 0.030 30/30 0.05 mm Notwhitened ≦20 (1000) 45 C2 0.031 30/30 0.15 mm Very slightly ≦20 (1000)whitened at the bottom 46 D2 0.023 24/30 0.30 mm Not whitened ≦20 (1000)47 E2 0.023 30/30 0.05 mm Not whitened ≦20 (1000) 48 PET/E2/PET 0.03730/30 0.10 mm Not whitened ≦10 (300/600/100) 49 E2/AD/EVOH/AD/E2 0.02530/30 0.10 mm Not whitened ≦20 (500/20/60/20/400) Comparative 23 H20.081 30/30 0.05 mm Not whitened ≦20 Example (1000) 24 I2 0.050 18/300.25 mm Not whitened ≧50 (1000) 25 J2 0.110 28/30 0.05 mm Clouded ≦5(1000) *Falling strength: Number of no cracked or leaking containers outof 30 containers

It can be seen from Tables 13 and 14 that the moisture permeability ofthe stretched blow molded containers of Examples 43 to 49 was 0.045g/(m²·24 h) or less, indicating excellent steam barrier properties.

The moisture permeability of the stretched blow molded container ofComparative Example 26 was 0.050 g/(m²⁰·24 h), indicating slightly poorsteam barrier properties.

On the other hand, the moisture permeability of the stretched blowmolded containers of Comparative Examples 23 and 25 was 0.080 g/(m²⁰·24h), indicating poor steam barrier properties.

No cracks or leaks were observed in the stretched blow molded containersof Examples 44, 45, and 47 to 49, and the stretched blow moldedcontainer of Comparative Example 23 in a test where 30 containers werecaused to fall from a height of 1 m, indicating excellent fallingstrength.

On the other hand, the stretched blow molded container of ComparativeExample 24 showed poor falling strength.

The stretched blow molded containers of Examples 43 to 45 and 47 to 49,and the stretched blow molded containers of Comparative Examples 23 and25 exhibited excellent blow moldability.

The stretched blow molded containers of Examples 43, 44, and 46 to 49,and the stretched blow molded containers of Comparative Examples 23 and24 exhibited remarkably excellent oil resistance. The stretched blowmolded container of Comparative Example 25 showed poor oil resistance.

The stretched blow molded containers of Examples 43 to 49 had a hazevalue of 20% or less, indicating their excellent transparency. Thestretched blow molded container of Example 48 particularly had a hazevalue of 10% or less, indicating very good transparency. The stretchedblow molded container of Comparative Example 24 had a haze value of 50%or more, indicating poor transparency.

Based on the above results, the blow molded containers of Examples 43 to49 can be regarded to be excellent in all performance, including steambarrier properties, mechanical properties, processability, oilresistance, and transparency demanded in recent years in the fields ofinformation processing, food industries, medical supplies, engineeringworks, and the like.

Example 50

The Antioxidant A was added to and dissolved in a colorless transparentsolution of a hydrogenated ring-open polymer (1) obtained in the samemanner as in Example 1 in an amount of 0.1 part by weight per 100 partsby weight of the polymer solid component.

The solution was filtered through a metal fiber filter (pore diameter:0.5 μm, manufactured by Nichidai Filter Corporation) and the filtratewas filtered through another filter Zeta Plus Filter 30S (pore diameter:0.5 to 1 μm manufactured by Quno Corp.). The resulting filtrate wasfurther filtered through still another metal fiber filter (porediameter: 0.2 μm, manufactured by Nichidai Filter Corporation) to removeforeign matter. The finally obtained filtrate was heated to 200° C.using a preheater and continuously supplied to a thin film dryer under apressure of 3 MPa (manufactured by Hitachi, Ltd.). The thin film dryerwas operated under conditions of a pressure of 13.4 kPa or less and atemperature of the concentrated polymer solution in the drier of 240° C.(first drying step).

Next, the concentrated solution was continuously removed from the thinfilm drier and supplied to another thin film drier of the same typeunder a pressure of 1.5 MPa while maintaining the temperature at 240° C.This dryer was operated under the conditions of a pressure of 0.7 kPaand a temperature of 240° C. (second drying step).

The polymer was continuously removed from the thin film drier in amelted state, extruded from a mold die in a class 100 clean room, cooledwith water, and cut using a pelletizer (OSP-2 manufactured by OsadaSeisakusho Co., Ltd.) to obtain pellets of a molding material (A).

The amount of organic substances released from the molding material (A)and the transition metal content of the molding material (A) weremeasured. The results are shown in Table 15.

(Preparation of Wafer Carrier)

The molding material (A) was injected using an injection molding machine(manufactured by Fanuc, Ltd.) under the conditions of a cylindertemperature of 240° C., a die temperature of 120° C., an injection speedof 50 cm³/s, an injection pressure of 1.47×10⁸ Pa, a support pressure of9.8×10⁷ Pa, and a back pressure of 6.9×10⁶ Pa to obtain an 8 inch wafercarrier (A) shown in FIG. 1.

The amount of increased foreign matter and heat resistance of theresulting wafer carrier (A) were evaluated. The results are shown inTable 15.

Example 51

A solution containing a hydrogenated ring-open polymer (15) obtained inthe same manner as in Example 10 was prepared. A molding material (B)was obtained in the same manner as in Example 50 using the solution ofthe hydrogenated ring-open polymer (15).

The amount of organic substances released from the molding material (B)and the transition metal content of the molding material (B) weremeasured. The results are shown in Table 15.

(Preparation of Wafer Carrier)

A wafer carrier (B) was prepared in the same manner as in Example 50,except for using the molding material (B) instead of the moldingmaterial (A).

The amount of increased foreign matter and heat resistance of theresulting wafer carrier (B) were evaluated. The results are shown inTable 15.

Example 52

A solution containing a hydrogenated ring-open polymer (11) obtained inthe same manner as in Example 6 was prepared. A molding material (C) wasobtained in the same manner as in Example 50 using the solution of thehydrogenated ring-open polymer (11).

The amount of organic substances released from the molding material (C)and the transition metal content of the molding material (C) weremeasured. The results are shown in Table 15.

(Preparation of Wafer Carrier)

A wafer carrier (C) was prepared in the same manner as in Example 50,except for using the molding material (C) instead of the moldingmaterial (A).

The amount of increased foreign matter and heat resistance of theresulting wafer carrier (C) were evaluated. The results are shown inTable 15.

Comparative Example 26

The Antioxidant A was added to a solution of a hydrogenated ring-openpolymer (20) obtained in the same manner as in Comparative Example 23 inan amount of 0.5 parts by weight per 100 parts by weight of the polymer.A molding material (D) was obtained in the same manner as in Example 50.

The amount of organic substances released from the resin composition (D)and the transition metal content of the resin composition (D) weremeasured. The results are shown in Table 15.

(Preparation of Wafer Carrier)

A wafer carrier (D) was prepared in the same manner as in Example 50,except that the molding material (D) was used instead of the moldingmaterial (A) and the cylinder temperature and the die temperature wererespectively 210° C. and 80° C.

The amount of increased foreign matter and heat resistance of theresulting wafer carrier (D) were evaluated. The results are shown inTable 15.

Comparative Example 27 Ring-Opening Copolymerization and HydrogenationReaction

Polymerization and hydrogenation reactions were carried out in the samemanner as in Comparative Example 23, except that6-methyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene(hereinafter referred to from time to time as “MDO”) was used instead of2-norbornene, and the amount of 1-hexene used was 0.40 parts by weight,and a hydrogenated ring-open polymer (21) was obtained.

(Properties of Polymer)

The degree of hydrogenation of the resulting hydrogenated ring-openpolymer (21) was 99.9%, the weight average molecular weight (Mw) was70,000, the molecular weight distribution (Mw/Mn) was 2.5, the glasstransition temperature was 140° C., and a melting point was notobserved.

(Preparation of Resin Composition)

A molding material (E) was obtained in the same manner as in Example 50using the solution of the hydrogenated ring-open polymer (21), exceptthat the thin film drier was operated at 260° C. in the first dryingstep and at 270° C. in the second drying step.

The amount of organic substances released from the molding material (E)and the transition metal content of the molding material (E) weremeasured. The results are shown in Table 15.

(Preparation of Wafer Carrier)

A wafer carrier (E) was prepared in the same manner as in Example 50,except that the molding material (E) was used instead of the moldingmaterial (A) and the cylinder temperature and the die temperature wererespectively 300° C. and 130° C.

The amount of increased foreign matter and heat resistance of theresulting wafer carrier (E) were evaluated. The results are shown inTable 15.

TABLE 15 Hydrogenated ring-open polymer Melting Isomer- OrganicTransition Heat Foreign Molding Monomer Mw/ point ization substancesmetal Wafer resis- matter material (wt %) No. Mw Mn (° C.) rate (%)(ppb) (ppm) carrier tance increase* Example 50 A 2-NB 1 82,200 2.9 140 56 <1 A Good 220 (100) 51 B 2-NB/DCPD 15 81,300 3.8 134 9 8 <1 B Good 210(96/4) 52 C 2-NB/MNB 11 100,000 2.9 136 8 6 <1 C Good 180 (98/2)Comparative 26 D 2-NB/DCPD 20 85,000 3.9 101 0 60 <1 D Bad 250 Example(89/11) 27 E MDO 21 70,000 2.5 140 — 35 <1 E Good 1800 (100) *Number offoreign matter particles

As can be seen from Table 15, the wafer carriers of Examples 50 to 52exhibited excellent heat resistance and the amounts of dischargedorganic substances and increased foreign matter were smaller than thecorresponding amounts of the wafer carriers of Comparative Examples 26and 27. On the other hand, the wafer carrier of Comparative Example 26exhibited poor heat resistance and the wafer carrier of ComparativeExample 27 exhibited a particularly large increase in the amount offoreign matter.

INDUSTRIAL APPLICABILITY

The hydrogenated ring-open polymer and the resin composition of thepresent invention are useful as a resin material for molding which isexcellent in all performance, including steam barrier properties, heatresistance, oil resistance, mechanical properties, transparency andprocessability demanded in recent years in the fields of informationprocessing, food industries, medical supplies, engineering works, andthe like.

Since the molded article of the present invention has excellent heatresistance, discharges only a small amount of organic substances, andgenerates only a small amount of foreign matter, the molded article canbe suitably used as a material for fabricating electron processinginstruments.

The resin film and sheet of the present invention are useful as a filmor a sheet used in the fields of information processing, foodindustries, medical supplies, engineering works, and the like, since theresin film and sheet exhibit excellent performance, including steambarrier properties, heat resistance, oil resistance, mechanicalproperties, transparency, and processability.

The multilayer laminate of the present invention is useful as a wrappingmaterial for toys, household goods, and the like, in addition to packingmaterial in the fields of foods, medical supplies, displays, energy, andother industrial fields. A packing material with a desired shape andsize can be prepared by secondary fabrication of the multilayer laminateof the present invention.

Due to the possession of excellent steam barrier properties and impactresistance, the packing material of the present invention is useful as amedical supply container and the like such as an infusion solution bag,a PTP (press through package), a syringe and the like.

The blister molded article of the present invention is useful as acontainer, a blister pack, or the like for medical supplies such as apress through package (PTP), a syringe, and the like; foods; precisioncomponents such as electric and electronic parts, semiconductor parts,and printed circuit boards; solar energy power generation systemcomponents; fuel cell components; alcohol-containing fuel systemcomponents; and the like.

Due to the possession of those various characteristics, the blow moldedcontainer of the present invention can be suitably used as variouscontainers demanded in recent years in the fields of food industries,medical supplies, engineering works, and the like.

1.-12. (canceled)
 13. A multilayer laminate having two or more resinlayers of which at least one layer is a layer of a hydrogenatednorbornene ring-open polymer obtained by hydrogenating 80% or more ofcarbon-carbon double bonds of a ring-open polymer which is obtained byring-opening polymerization of 2-norbornene or a monomer mixture of2-norbornene and a substituent-containing norbornene monomer, theproportion of a repeating unit (A) derived from the 2-norbornene withrespect to all repeating units being 90 to 100 wt % and the proportionof a repeating unit (B) derived from the substituent-containingnorbornene monomer with respect to all repeating units being 0 to 10 wt%, and the hydrogenated norbornene ring-open polymer having a meltingpoint of 110 to 145° C.
 14. The multilayer laminate according to claim13, wherein at least one layer is a layer containing a gas barrierresin.
 15. The multilayer laminate according to claim 14, wherein thegas barrier resin is an ethylene-vinyl alcohol copolymer.
 16. Themultilayer laminate according to claim 13, wherein at least one layer isa layer containing at least one resin selected from the group consistingof a polyolefin resin, a polyamide resin, and a polyester resin.
 17. Apacking material obtained by fabricating the multilayer laminateaccording to claim
 13. 18.-26. (canceled)